Heterocycle-substituted bicyclic azole pesticides

ABSTRACT

Disclosed are compounds of Formula 1, including all geometric and stereoisomers, N-oxides, and salts thereof, 
                         
wherein
         Q is       

                         
and A, R 1 , m, X 1 , X 2 , Y 1 , Y 2 , Y 3  and R 5a  are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling an invertebrate pest comprising contacting the invertebrate pest or its environment with a biologically effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain substituted bicyclic azoles, theirN-oxides, salts and compositions suitable for agronomic and nonagronomicuses, and methods of their use for controlling invertebrate pests suchas arthropods in both agronomic and nonagronomic environments.

BACKGROUND OF THE INVENTION

The control of invertebrate pests is extremely important in achievinghigh crop efficiency. Damage by invertebrate pests to growing and storedagronomic crops can cause significant reduction in productivity andthereby result in increased costs to the consumer. The control ofinvertebrate pests in forestry, greenhouse crops, ornamentals, nurserycrops, stored food and fiber products, livestock, household, turf, woodproducts, and public and animal health is also important. Many productsare commercially available for these purposes, but the need continuesfor new compounds that are more effective, less costly, less toxic,environmentally safer or have different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allgeometric and stereoisomers), N-oxides, and salts thereof, andcompositions containing them and their use for controlling invertebratepests:

wherein

-   -   Q is

-   -   A is CH, CR¹ or N;    -   each R¹ is independently halogen, cyano, nitro, C₁-C₄ alkyl,        C₁-C₄ haloalkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio        or C₁-C₄ haloalkylthio;    -   m is 0, 1, 2 or 3;    -   X¹ is —C(R²)═C(R³)—, —C(R³)═C(R²)—, —C(R²)═N— or —N═C(R²)—; and        X² is O, S or NR³; or    -   X¹ is O, S or NR³; and X² is —C(R²)═C(R³)—; or    -   X¹ is NR^(2a); and X² is —C(R³)═C(R³)—;    -   R² is C(═Z)R¹¹, C(═Z)NR⁶R⁷, L¹C(═Z)R¹¹, L¹C(═Z)NR⁶R⁷ or LQ^(a);        or C₁-C₄ alkyl substituted with C(═Z)R¹¹ or C(═Z)NR⁶R⁷;    -   R^(2a) is C(═Z)R¹¹, C(═Z)NR⁶R⁷ or Q^(a); or C₁-C₄ alkyl        substituted with C(═Z)R¹¹ or C(═Z)NR⁶R⁷;    -   L is direct bond, O, S(O)_(n), NR⁸ or C(═Z);    -   L¹ is O or NR⁸;    -   each Z is independently O or S;    -   each R³ is independently H, halogen, cyano, nitro, C₁-C₄ alkyl,        C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;    -   Y¹ is O, S or NR⁴;    -   Y² is N or CR^(5a);    -   Y³ is N or CR^(5b);    -   R⁴ is H or C₁-C₄ alkyl;    -   R^(5a) is H, halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;    -   R^(5b) is H, halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄ haloalkoxy;    -   R⁶ is H, NR¹⁵R¹⁶, OR¹⁷, C(═NR¹⁰)R¹¹, C(O)OR²¹, C(O)NR¹⁵R¹⁶,        C(O)R²², S(O)_(n)R²³ or Q^(b); or C₁-C₆ alkyl, C₃-C₆ cycloalkyl,        C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or        substituted with at least one R^(x);    -   R⁷ is H or Q^(b); or C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆        alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with        at least one R^(x); or    -   R⁶ and R⁷ are taken together with the nitrogen atom to which        they are attached to form a 3- to 10-membered ring containing        ring members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, said        ring being unsubstituted or substituted with up to 4 R^(x); or    -   R⁶ and R⁷ are taken together as ═S(O)_(p)R¹⁸R¹⁹ or        ═S(═NR²⁰)R¹⁸R¹⁹;    -   each R^(x) is independently halogen, cyano, nitro, hydroxy,        C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy,        C₁-C₆ haloalkoxy, C₃-C₆ cycloalkoxy, C(═NR¹⁰)R¹¹, C(O)OR²¹,        C(O)NR¹⁵R¹⁶, OC(O)R²², NR²⁵R²⁶, NR²⁴C(O)R²², C(O)R²²,        S(O)_(n)R²³, Si(R²⁸)₃, OSi(R²⁸)₃ or Q^(b);    -   R⁸ is H, C(O)OR²¹, C(O)NR¹⁵R¹⁶, C(O)R²², S(O)_(n)R²³ or Q^(b);        or C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆        alkynyl, each unsubstituted or substituted with at least one        R^(x);    -   R⁹ is H, C(═NR¹⁰)R¹¹, OR²¹ or NR¹⁵R¹⁶; or C₁-C₆ alkyl, C₃-C₆        cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted        or substituted with at least one R^(x); or phenyl, phenoxy or a        5- or 6-membered heterocyclic aromatic ring, each unsubstituted        or substituted with at least one substituent independently        selected from the group consisting of halogen, cyano, nitro,        C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and        C₁-C₄ haloalkoxy; or a 3- to 6-membered heterocyclic        non-aromatic ring, each ring containing ring members selected        from carbon atoms and up to 3 heteroatoms independently selected        from one oxygen atom, one sulfur atom, and up to 2 nitrogen        atoms, wherein up to 1 carbon atom ring member is independently        selected from C(═O) and C(═S) and the sulfur atom ring member is        selected from S, S(O) or S(O)₂, each ring being unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R¹⁰ is independently OR¹², S(O)_(n)R¹³ or NHR¹⁴;    -   each R¹¹ is independently H; or C₁-C₆ alkyl, C₃-C₆ cycloalkyl,        C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or        substituted with at least one R^(x); or C₁-C₆ alkoxy, C₁-C₆        haloalkoxy, C₃-C₆ cycloalkoxy, C(O)OR²¹, C(O)NR¹⁵R¹⁶, C(O)R²² or        Q^(b);    -   each R¹² is independently C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C(O)R²², S(O)_(n)R¹³ or Q^(b);    -   each R¹³ is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl;    -   R¹⁴ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C(O)R²²        or C(O)OR²¹; or phenyl, unsubstituted or substituted with at        least one substituent independently selected from the group        consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹⁵ is independently H, C₁-C₆ alkyl, C₁-C₄ haloalkyl,        C(O)R²⁷ or S(O)₂R²⁷; or phenyl or a 5- or 6-membered        heterocyclic aromatic ring, each unsubstituted or substituted        with at least one substituent independently selected from the        group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹⁶ is independently H, C₁-C₆ alkyl or C₁-C₄ haloalkyl; or    -   R¹⁵ and R¹⁶ are taken together with the nitrogen atom to which        they are attached to form a 3- to 7-membered ring containing        ring members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, said        ring being unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   R¹⁷ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹⁸ is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R¹⁹ is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or    -   R¹⁸ and R¹⁹ are taken together with the sulfur atom to which        they are attached to form a ring;    -   R²⁰ is H, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C(O)R²²; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R²¹ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆        cycloalkyl or C₃-C₆ halocycloalkyl; or phenyl, unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R²² is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆        cycloalkyl or C₃-C₆ halocycloalkyl; or phenyl, unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R²³ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆        cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆ cycloalkylalkyl or C₃-C₆        halocycloalkylalkyl; or phenyl, unsubstituted or substituted        with at least one substituent independently selected from the        group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R²⁴ is independently C₁-C₄ alkyl;    -   each R²⁵ is independently H, C₁-C₄ alkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R²⁶ is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl; or        phenyl, unsubstituted or substituted with at least one        substituent independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or    -   R²⁵ and R²⁶ are independently taken together with the nitrogen        atom to which they are attached to form a 3- to 7-membered ring        containing ring members selected from carbon atoms and up to 2        heteroatoms independently selected from one oxygen atom, one        sulfur atom, and up to 2 nitrogen atoms, wherein up to 2 carbon        atom ring members are independently selected from C(═O) and        C(═S) and the sulfur atom ring member is selected from S, S(O)        or S(O)₂, said ring being unsubstituted or substituted with at        least one substituent independently selected from the group        consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆        cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each R²⁷ is independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆        alkoxy, C₁-C₆ haloalkoxy or NR²⁹R³⁰; or phenyl or a 5- or        6-membered heterocyclic aromatic ring, each unsubstituted or        substituted with at least one substituent independently selected        from the group consisting of halogen, cyano, nitro, C₁-C₄ alkyl,        C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄        haloalkoxy;    -   each R²⁸ is independently C₁-C₆ alkyl, C₃-C₆ cycloalkyl or        phenyl;    -   each R²⁹ is independently H or Q^(b); or C₁-C₆ alkyl, C₃-C₆        cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted        or substituted with at least one substituent independently        selected from the group consisting of halogen, cyano, nitro,        C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and        C₁-C₄ haloalkoxy;    -   each R³⁰ is independently H or Q^(b); or C₁-C₆ alkyl, C₃-C₆        cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted        or substituted with at least one substituent independently        selected from the group consisting of halogen, cyano, nitro,        C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and        C₁-C₄ haloalkoxy; or    -   R²⁹ and R³⁰ are taken together with the nitrogen atom to which        they are attached to form a 3- to 10-membered ring containing        ring members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, said        ring being unsubstituted or substituted with up to 4        substituents independently selected from the group consisting of        halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄        haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   Q^(a) is a 5- to 10-membered aromatic ring or ring system, each        ring or ring system containing ring members selected from carbon        atoms and up to 3 heteroatoms independently selected from one        oxygen atom, one sulfur atom, and up to 3 nitrogen atoms,        wherein up to 2 carbon atom ring members are independently        selected from C(═O) and C(═S) and the sulfur atom ring member is        selected from S, S(O) or S(O)₂, each ring or ring system being        unsubstituted or substituted with at least one R^(x); or a 3- to        6-membered partially saturated ring, each ring containing ring        members selected from carbon atoms and up to 2 heteroatoms        independently selected from one oxygen atom, one sulfur atom,        and up to 2 nitrogen atoms, wherein up to 2 carbon atom ring        members are independently selected from C(═O) and C(═S) and the        sulfur atom ring member is selected from S, S(O) or S(O)₂, each        ring unsubstituted or substituted with at least one substituent        independently selected from the group consisting of halogen,        cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,        C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each Q^(b) is independently phenyl, a 5- or 6-membered        heterocyclic aromatic ring or a 3- to 6-membered heterocyclic        non-aromatic ring, each ring containing ring members selected        from carbon atoms and up to 2 heteroatoms independently selected        from one oxygen atom, one sulfur atom, and up to 2 nitrogen        atoms, wherein up to 2 carbon atom ring members are        independently selected from C(═O) and C(═S) and the sulfur atom        ring member is selected from S, S(O) or S(O)₂, each ring        unsubstituted or substituted with at least one substituent        independently selected from the group consisting of halogen,        cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,        C₁-C₄ alkoxy and C₁-C₄ haloalkoxy;    -   each n is independently 0, 1 or 2; and    -   p is 1 or 2.

This invention also provides a composition comprising a compound ofFormula 1, an N-oxide or a salt thereof, and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents. In one embodiment, this invention alsoprovides a composition for controlling an invertebrate pest comprising acompound of Formula 1, an N-oxide or a salt thereof, and at least oneadditional component selected from the group consisting of surfactants,solid diluents and liquid diluents, said composition optionally furthercomprising at least one additional biologically active compound oragent.

This invention further provides a spray composition for controlling aninvertebrate pest comprising a compound of Formula 1, an N-oxide or asalt thereof, or the compositions described above, and a propellant.This invention also provides a bait composition for controlling aninvertebrate pest comprising a compound of Formula 1, an N-oxide or asalt thereof, or the compositions described in the embodiments above,one or more food materials, optionally an attractant, and optionally ahumectant.

This invention further provides a trap device for controlling aninvertebrate pest comprising said bait composition and a housing adaptedto receive said bait composition, wherein the housing has at least oneopening sized to permit the invertebrate pest to pass through theopening so the invertebrate pest can gain access to said baitcomposition from a location outside the housing, and wherein the housingis further adapted to be placed in or near a locus of potential or knownactivity for the invertebrate pest.

This invention provides a method for controlling an invertebrate pestcomprising contacting the invertebrate pest or its environment with abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, (e.g., as a composition described herein). Thisinvention also relates to such method wherein the invertebrate pest orits environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, and at least one additional component selected from thegroup consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising a biologically effectiveamount of at least one additional biologically active compound or agent.

This invention also provides a method for protecting a seed from aninvertebrate pest comprising contacting the seed with a biologicallyeffective amount of a compound of Formula 1, an N-oxide or a saltthereof, (e.g., as a composition described herein). This invention alsorelates to the treated seed. This invention further provides a methodfor protecting an animal from an invertebrate parasitic pest comprisingadministering to the animal a parasiticidally effective amount of acompound of Formula 1, an N-oxide or a salt thereof, (e.g., as acomposition described herein). This invention also provides for the useof a compound of Formula 1, an N-oxide or a salt thereof, (e.g., as acomposition described herein) in protecting an animal from aninvertebrate pest.

This invention also provides a method for increasing vigor of a cropplant comprising contacting the crop plant, the seed from which the cropplant is grown or the locus (e.g., growth medium) of the crop plant witha biologically effective amount of a compound of Formula 1 (e.g., as acomposition described herein).

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process or method that comprises alist of elements is not necessarily limited to only those elements butmay include other elements not expressly listed or inherent to suchcomposition, mixture, process or method.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition or method that includes materials, steps, features,components, or elements, in addition to those literally disclosed,provided that these additional materials, steps, features, components,or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in this disclosure, the term “invertebrate pest” includesarthropods, gastropods, nematodes and helminths of economic importanceas pests. The term “arthropod” includes insects, mites, spiders,scorpions, centipedes, millipedes, pill bugs and symphylans. The term“gastropod” includes snails, slugs and other Stylommatophora. The term“nematode” includes members of the phylum Nematoda, such as phytophagousnematodes and helminth nematodes parasitizing animals. The term“helminth” includes all of the parasitic worms, such as roundworms(phylum Nematoda), heartworms (phylum Nematoda, class Secernentea),flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans(phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, classCestoda).

In the context of this disclosure “invertebrate pest control” meansinhibition of invertebrate pest development (including mortality,feeding reduction, and/or mating disruption), and related expressionsare defined analogously.

The term “agronomic” refers to the production of field crops such as forfood and fiber and includes the growth of maize or corn, soybeans andother legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice),leafy vegetables (e.g., lettuce, cabbage, and other cole crops),fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers andcucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g.,pome, stone and citrus), small fruit (e.g., berries and cherries) andother specialty crops (e.g., canola, sunflower and olives).

The term “nonagronomic” refers to other than field crops, such ashorticultural crops (e.g., greenhouse, nursery or ornamental plants notgrown in a field), residential, agricultural, commercial and industrialstructures, turf (e.g., sod farm, pasture, golf course, lawn, sportsfield, etc.), wood products, stored product, agro-forestry andvegetation management, public health (i.e. human) and animal health(e.g., domesticated animals such as pets, livestock and poultry,undomesticated animals such as wildlife) applications.

The term “crop vigor” refers to rate of growth or biomass accumulationof a crop plant. An “increase in vigor” refers to an increase in growthor biomass accumulation in a crop plant relative to an untreated controlcrop plant. The term “crop yield” refers to the return on crop material,in terms of both quantity and quality, obtained after harvesting a cropplant. An “increase in crop yield” refers to an increase in crop yieldrelative to an untreated control crop plant.

The term “biologically effective amount” refers to the amount of abiologically active compound (e.g., a compound of Formula 1) sufficientto produce the desired biological effect when applied to (i.e. contactedwith) an invertebrate pest to be controlled or its environment, or to aplant, the seed from which the plant is grown, or the locus of the plant(e.g., growth medium) to protect the plant from injury by theinvertebrate pest or for other desired effect (e.g., increasing plantvigor).

The position of the variable R¹ in the structure of Formula 1 isdescribed by the numbering system shown below.

A wavy line in a structure fragment denotes the attachment point of thefragment to the remainder of the molecule. For example, when thevariable Q in Formula 1 is defined as Q-1, the wavy line bisecting thebond in Q-1 means that Q-1 is attached to the remainder of the structureof Formula 1 at said position, as shown below.

In structures Q-1, Q-2, Q-3 and Q-4, the variables X¹ and X² are definedas: X¹ is —C(R²)═C(R³)—, —C(R³)═C(R²)—, —C(R²)═N— or —N═C(R²)—; and X²is O, S or NR³; or X¹ is O, S or NR³; and X² is —C(R²)═C(R³)—; or X¹ isNR^(2a); and X² is —C(R³)═C(R³)—. This definition of X¹ and X² describessixteen possible combinations of X¹-X², shown in the table below.

Combination X¹ X² X¹-X² 1 —C(R²)═C(R³)— O —C(R²)═C(R³)O— 2 —C(R²)═C(R³)—S —C(R²)═C(R³) S— 3 —C(R²)═C(R³)— NR³ —C(R²)═C(R³)N(R³)— 4 —C(R³)═C(R²)—O —C(R³)═C(R²)O— 5 —C(R³)═C(R²)— S —C(R³)═C(R²)S— 6 —C(R³)═C(R²)— NR³—C(R³)═C(R²)N(R³)— 7 —C(R²)═N— O —C(R²)═NO— 8 —C(R²)═N— S —C(R²)═NS— 9—C(R²)═N— NR³ —C(R²)═NN(R³)— 10 —N═C(R²)— O —N═C(R²)O— 11 —N═C(R²)— S—N═C(R²)S— 12 —N═C(R²)— NR³ —N═C(R²)N(R³)— 13 O —C(R²)═C(R³)——OC(R²)═C(R³)— 14 S —C(R²)═C(R³)— —SC(R²)═C(R³)— 15 NR³ —C(R²)═C(R³)——N(R³)C(R²)═C(R³)— 16 NR^(2a) —C(R³)═C(R³)— —N(R^(2a))C(R³)═C(R³)—

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl, such as, methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” can also include moietiescomprised of multiple triple bonds such as 2,5-hexadiynyl.

“Alkoxy” includes, for example, methoxy, ethoxy, n-propyloxy,isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.“Alkylthio” includes branched or straight-chain alkylthio moieties suchas methylthio, ethylthio, and the different propylthio, butylthio,pentylthio and hexylthio isomers.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl.

The term “halogen”, either alone or in compound words such as“haloalkyl”, or when used in descriptions such as “alkyl substitutedwith halogen” includes fluorine, chlorine, bromine or iodine. Further,when used in compound words such as “haloalkyl”, or when used indescriptions such as “alkyl substituted with halogen” said alkyl may bepartially or fully substituted with halogen atoms which may be the sameor different. Examples of“haloalkyl” or “alkyl substituted with halogen”include F₃C—, ClCH₂—, CF₃CH₂— and CF₃CCl₂—. The terms “halocycloalkyl”,“haloalkoxy”, “haloalkylthio”, “haloalkenyl”, “haloalkynyl”, and thelike, are defined analogously to the term “haloalkyl”. Examplesof“haloalkoxy” include CF₃O—, CCl₃CH₂O—, HCF₂CH₂CH₂O— and CF₃CH₂O—.Examples of“haloalkylthio” include CCl₃S—, CF₃S—, CCl₃CH₂S— andClCH₂CH₂CH₂S—.

The chemical abbreviations S(O) and S(═O) as used herein represent asulfinyl moiety. The chemical abbreviations SO₂, S(O)₂ and S(═O)₂ asused herein represent a sulfonyl moiety. The chemical abbreviations C(O)and C(═O) as used herein represent a carbonyl moiety. The chemicalabbreviations CO₂, C(O)O and C(═O)O as used herein represent anoxycarbonyl moiety. “CHO” means formyl.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 6. Forexample, C₁-C₄ alkylsulfonyl designates methylsulfonyl throughbutylsulfonyl; C₂ alkoxyalkyl designates CH₃OCH₂—; C₃ alkoxyalkyldesignates, for example, CH₃CH(OCH₃)—, CH₃OCH₂CH₂— or CH₃CH₂OCH₂—; andC₄ alkoxyalkyl designates the various isomers of an alkyl groupsubstituted with an alkoxy group containing a total of four carbonatoms, examples including CH₃CH₂CH₂OCH₂— and CH₃CH₂OCH₂CH₂—.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents, e.g., (R¹)_(m), m is 0, 1, 2 or 3.Further, when the subscript indicates a range, e.g. (R)_(i-j), then thenumber of substituents may be selected from the integers between i and jinclusive. When a group contains a substituent which can be hydrogen,for example R³ or R⁴, then when this substituent is taken as hydrogen,it is recognized that this is equivalent to said group beingunsubstituted. When a variable group is shown to be optionally attachedto a position, for example (R¹)_(m) wherein m may be 0, then hydrogenmay be at the position even if not recited in the variable groupdefinition. When one or more positions on a group are said to be “notsubstituted” or “unsubstituted”, then hydrogen atoms are attached totake up any free valency.

Unless otherwise indicated, a “ring” or “ring system” as a component ofFormula 1 (e.g., substituent Q^(a)) is carbocyclic or heterocyclic. Theterm “ring system” denotes two or more fused rings. The terms “bicyclicring system” and “fused bicyclic ring system” denote a ring systemconsisting of two fused rings, which can be “ortho-fused”, “bridgedbicyclic” or “spirobicyclic”. An “ortho-fused bicyclic ring system”denotes a ring system wherein the two constituent rings have twoadjacent atoms in common. A “bridged bicyclic ring system” is formed bybonding a segment of one or more atoms to nonadjacent ring members of aring. A “spirobicyclic ring system” is formed by bonding a segment oftwo or more atoms to the same ring member of a ring. The term “fusedheterobicyclic ring system” denotes a fused bicyclic ring system inwhich at least one ring atom is not carbon. The term “ring member”refers to an atom or other moiety (e.g., C(═O), C(═S), S(O) or S(O)₂)forming the backbone of a ring or ring system.

The terms “carbocyclic ring”, “carbocycle” or “carbocyclic ring system”denote a ring or ring system wherein the atoms forming the ring backboneare selected only from carbon. The terms “heterocyclic ring”,“heterocycle” or “heterocyclic ring system” denote a ring or ring systemin which at least one atom forming the ring backbone is not carbon,e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring containsno more than 4 nitrogens, no more than 2 oxygens and no more than 2sulfurs. Unless otherwise indicated, a carbocyclic ring or heterocyclicring can be a saturated or unsaturated ring. “Saturated” refers to aring having a backbone consisting of atoms linked to one another bysingle bonds; unless otherwise specified, the remaining atom valencesare occupied by hydrogen atoms. Unless otherwise stated, an “unsaturatedring” may be partially unsaturated or fully unsaturated. The expression“fully unsaturated ring” means a ring of atoms in which the bondsbetween atoms in the ring are single or double bonds according tovalence bond theory and furthermore the bonds between atoms in the ringinclude as many double bonds as possible without double bonds beingcumulative (i.e. no C═C═C or C═C═N). The term “partially unsaturatedring” denotes a ring comprising at least one ring member bonded to anadjacent ring member through a double bond and which conceptuallypotentially accommodates a number of non-cumulated double bonds betweenadjacent ring members (i.e. in its fully unsaturated counterpart form)greater than the number of double bonds present (i.e. in its partiallyunsaturated form).

Unless otherwise indicated, heterocyclic rings and ring systems can beattached through any available carbon or nitrogen by replacement of ahydrogen on said carbon or nitrogen.

“Aromatic” indicates that each of the ring atoms is essentially in thesame plane and has a p-orbital perpendicular to the ring plane, and inwhich (4n+2) π electrons, where n is a positive integer, are associatedwith the ring to comply with Hückel's rule. The term “aromatic ringsystem” denotes a carbocyclic or heterocyclic ring system in which atleast one ring of the ring system is aromatic. When a fully unsaturatedcarbocyclic ring satisfies Hückel's rule, then said ring is also calledan “aromatic ring” or “aromatic carbocyclic ring”.

The term “aromatic carbocyclic ring system” denotes a carbocyclic ringsystem in which at least one ring of the ring system is aromatic. When afully unsaturated heterocyclic ring satisfies Hückel's rule, then saidring is also called a “heteroaromatic ring”, “aromatic heterocyclicring” or “heterocyclic aromatic ring”. The term “aromatic heterocyclicring system” denotes a heterocyclic ring system in which at least onering of the ring system is aromatic. The term “nonaromatic ring system”denotes a carbocyclic or heterocyclic ring system that may be fullysaturated, as well as partially or fully unsaturated, provided that noneof the rings in the ring system are aromatic. The term “nonaromaticcarbocyclic ring system” denotes a carbocyclic ring in which no ring inthe ring system is aromatic. The term “nonaromatic heterocyclic ringsystem” denotes a heterocyclic ring system in which no ring in the ringsystem is aromatic.

The term “optionally substituted” in connection with the heterocyclicrings refers to groups which are unsubstituted or have at least onenon-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. As used herein, thefollowing definitions shall apply unless otherwise indicated. The term“optionally substituted” is used interchangeably with the phrase“substituted or unsubstituted” or with the term “(un)substituted.”Unless otherwise indicated, an optionally substituted group may have asubstituent at each substitutable position of the group, and eachsubstitution is independent of the other.

When a substituent is a 5- or 6-membered nitrogen-containingheterocyclic ring, it may be attached to the remainder of Formula 1though any available carbon or nitrogen ring atom, unless otherwisedescribed. As noted above, Q^(a) can be (among others) phenyl optionallysubstituted with one or more substituents selected from a group ofsubstituents as defined in the Summary of Invention. An example ofphenyl optionally substituted with one to five substituents is the ringillustrated as U-1 in Exhibit 1, wherein R^(v) is R^(x) as defined inthe Summary of the Invention for Q^(a) and r is an integer from 0 to 5.

As noted above, Q^(b) can be (among others) a 5- or 6-memberedheterocyclic aromatic ring, optionally substituted with one or moresubstituents selected from a group of substituents as defined in theSummary of Invention. Examples of a 5- or 6-membered unsaturatedaromatic heterocyclic ring optionally substituted with from one or moresubstituents include the rings U-2 through U-61 illustrated in Exhibit 1wherein R^(v) is any substituent as defined in the Summary of theInvention for Q^(b) and r is an integer from 0 to 4, limited by thenumber of available positions on each U group. As U-29, U-30, U-36,U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one availableposition, for these U groups r is limited to the integers 0 or 1, and rbeing 0 means that the U group is unsubstituted and a hydrogen ispresent at the position indicated by (R^(v))_(r).

As noted above, Q^(a) can be (among others) an 8-, 9- or 10-memberedortho-fused bicyclic ring system optionally substituted with one or moresubstituents selected from a group of substituents as defined in theSummary of Invention. Examples of 8-, 9- or 10-membered ortho-fusedbicyclic ring system optionally substituted with from one or moresubstituents include the rings U-81 through U-123 illustrated in Exhibit3 wherein R^(v) is any substituent as defined in the Summary of theInvention for Q^(a), and r is typically an integer from 0 to 4.

Although R^(v) groups are shown in the structures U-1 through U-123, itis noted that they do not need to be present since they are optionalsubstituents. Note that when R^(v) is H when attached to an atom, thisis the same as if said atom is unsubstituted. The nitrogen atoms thatrequire substitution to fill their valence are substituted with H orR^(v). Note that when the attachment point between (R^(v))_(r) and the Ugroup is illustrated as floating, (R^(v))_(r) can be attached to anyavailable carbon atom or nitrogen atom of the U group. Note that whenthe attachment point on the U group is illustrated as floating, the Ugroup can be attached to the remainder of Formula 1 through anyavailable carbon or nitrogen of the U group by replacement of a hydrogenatom. Note that some U groups can only be substituted with less than 4R^(v) groups (e.g., U-2 through U-5, U-7 through U-48, and U-52 throughU-61).

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers.Stereoisomers are isomers of identical constitution but differing in thearrangement of their atoms in space and include enantiomers,diastereomers, cis-trans isomers (also known as geometric isomers) andatropisomers. Atropisomers result from restricted rotation about singlebonds where the rotational barrier is high enough to permit isolation ofthe isomeric species. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. For a comprehensive discussion of all aspects ofstereoisomerism, see Ernest L. Eliel and Samuel H. Wilen,Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

This invention comprises all stereoisomers, conformational isomers andmixtures thereof in all proportions as well as isotopic forms such asdeuterated compounds.

One skilled in the art will appreciate that not all nitrogen-containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen-containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and 3-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethyldioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of invertebrate pests.The salts of the compounds of Formula 1 include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids. When a compound of Formula 1 contains an acidic moiety such as acarboxylic acid or phenol, salts also include those formed with organicor inorganic bases such as pyridine, triethylamine or ammonia, oramides, hydrides, hydroxides or carbonates of sodium, potassium,lithium, calcium, magnesium or barium. Accordingly, the presentinvention comprises compounds selected from Formula 1, N-oxides andsuitable salts thereof.

Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides,and salts thereof, typically exist in more than one form, and Formula 1thus includes all crystalline and non-crystalline forms of the compoundsthat Formula 1 represents. Non-crystalline forms include embodimentswhich are solids such as waxes and gums as well as embodiments which areliquids such as solutions and melts. Crystalline forms includeembodiments which represent essentially a single crystal type andembodiments which represent a mixture of polymorphs (i.e. differentcrystalline types). The term “polymorph” refers to a particularcrystalline form of a chemical compound that can crystallize indifferent crystalline forms, these forms having different arrangementsand/or conformations of the molecules in the crystal lattice. Althoughpolymorphs can have the same chemical composition, they can also differin composition due to the presence or absence of co-crystallized wateror other molecules, which can be weakly or strongly bound in thelattice. Polymorphs can differ in such chemical, physical and biologicalproperties as crystal shape, density, hardness, color, chemicalstability, melting point, hygroscopicity, suspensibility, dissolutionrate and biological availability. One skilled in the art will appreciatethat a polymorph of a compound represented by Formula 1 can exhibitbeneficial effects (e.g., suitability for preparation of usefulformulations, improved biological performance) relative to anotherpolymorph or a mixture of polymorphs of the same compound represented byFormula 1. Preparation and isolation of a particular polymorph of acompound represented by Formula 1 can be achieved by methods known tothose skilled in the art including, for example, crystallization usingselected solvents and temperatures. Compounds of this invention mayexist as one or more crystalline polymorphs. This invention comprisesboth individual polymorphs and mixtures of polymorphs, includingmixtures enriched in one polymorph relative to others. For acomprehensive discussion of polymorphism see R. Hilfiker, Ed.,Polymorphism In the Pharmaceutical Industry, Wiley-VCH, Weinheim, 2006.

Embodiments of the present invention as described in the Summary of theInvention include those described below. In the following Embodiments,reference to “a compound of Formula 1” includes the definitions ofsubstituents specified in the Summary of the Invention unless furtherdefined in the Embodiments.

-   -   Embodiment 1. A compound of Formula 1 wherein Q is Q-2 or Q-3.    -   Embodiment 1a. A compound of Formula 1 wherein Q is Q-2.    -   Embodiment 1b. A compound of Embodiment 1a wherein Y² is        CR^(5a).    -   Embodiment 1c. A compound of Formula 1 wherein Q is Q-3.    -   Embodiment 2. A compound of Formula 1 wherein A is CH, CR¹ or N,        and R¹ is halogen.    -   Embodiment 2a. A compound of Embodiment 2 wherein A is CH, CF or        N.    -   Embodiment 2b. A compound of Embodiment 2 wherein A is CF or N.    -   Embodiment 2c. A compound of Embodiment 2 wherein A is CH or CF.    -   Embodiment 2d. A compound of Embodiment 2 wherein A is CH.    -   Embodiment 2e. A compound of Embodiment 2 wherein A is N.    -   Embodiment 3. A compound of any of Embodiments 1-2e wherein Q is        Q-3.    -   Embodiment 3a. A compound of Formula 1 wherein Q is Q-3 and A is        CH.    -   Embodiment 3b. A compound of Formula 1 wherein Q is Q-3; and Y³        is CR^(5b).    -   Embodiment 3b. A compound of Formula 1 wherein Q is Q-3; and Y³        is CR⁵H.    -   Embodiment 3c. A compound of Formula 1 wherein Q is Q-3; and Y³        is CH.    -   Embodiment 4. A compound of Formula 1 or any of Embodiments 1-3a        wherein m is 1, and R¹ is C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄        alkoxy or halogen.    -   Embodiment 4a. A compound of Embodiment 4 wherein R¹ is CF₃,        OMe, Me, or F.    -   Embodiment 4b. A compound of Embodiment 4a wherein R¹ is CF₃,        OMe, Me, or F, and is in the 4-position.    -   Embodiment 4c. A compound of Embodiment 4b wherein R¹ is CF₃,        and is in the 4-position.    -   Embodiment 5. A compound of Formula 1 or any of Embodiments 1-3a        wherein m is 0.    -   Embodiment 5a. A compound of Formula 1 or any of Embodiments        1-3c wherein A is CH or CF; and m is 0.    -   Embodiment 6. A compound of Formula 1 or any of Embodiments 1-5        wherein X¹ is —C(R²)═C(R³)—, —C(R³)═C(R²)— or —N═C(R²)—; and X²        is O, S or NR³.    -   Embodiment 6a. A compound of Embodiment 6 wherein X¹ is        —C(R²)═C(R³)— or —C(R³)═C(R²)—; and X² is O, S or NR³.    -   Embodiment 6b. A compound of Formula 1 or any of Embodiments 1-6        wherein X¹ is —C(R²)═C(R³)—, —C(R³)═C(R²)— or —N═C(R²)—; and X²        is O or S.    -   Embodiment 6c. A compound of Embodiment 6b wherein X¹ is        —C(R²)═C(R³)— or —C(R³)═C(R²)—; and X² is O or S.    -   Embodiment 7. A compound of Formula 1 or any of Embodiments 1-6c        wherein each R³ is independently H or halogen.    -   Embodiment 7a. A compound of Embodiment 7 wherein each R³ is        independently H or F.    -   Embodiment 7b. A compound of Embodiment 7a wherein each R³ is H.    -   Embodiment 8. A compound of Formula 1 or any of Embodiments 1-7b        wherein R² is C(═Z)NR⁶R⁷ or LQ^(a).    -   Embodiment 8a. A compound of Formula 1 or any of Embodiments        1-7b wherein R² is C(═Z)NR⁶R⁷.    -   Embodiment 8b. A compound of Formula 1 or any of Embodiments        1-7b wherein R² is LQ^(a).    -   Embodiment 8c. A compound of Formula 1 or any of Embodiments        1-7b wherein R² is C(═Z)NR⁶R⁷ or LQ^(a); and L is a direct bond.    -   Embodiment 8d. A compound of Formula 1 or any of Embodiments        1-7b wherein R² is LQ^(a); and L is a direct bond.    -   Embodiment 8e. A compound of Formula 1 or any of Embodiments        1-7b wherein R² is C(═Z)NR⁶R⁷; and R⁶ is C₁-C₆ alkyl substituted        with at least one R^(x).    -   Embodiment 8f. A compound of Formula 1 or any of Embodiments        1-7b wherein R² is C(═Z)NR⁶R⁷; R⁶ is C₁-C₆ alkyl substituted        with at least one R^(x); and one R^(x) is C(O)NR¹⁵R¹⁶.    -   Embodiment 9. A compound of Formula 1 wherein R² is LQ^(a); L is        a direct bond; and Q^(a) is phenyl, unsubstituted or substituted        with at least one R^(x).    -   Embodiment 9a. A compound of Formula 1 wherein R² is LQ^(a); L        is a direct bond; and Q^(a) is a 5- or 6-membered heteroaromatic        ring, each ring containing ring members selected from carbon        atoms and up to 3 heteroatoms independently selected from one        oxygen atom, one sulfur atom, and up to 3 nitrogen atoms, each        ring being unsubstituted or substituted with at least one R^(x).    -   Embodiment 9b. A compound of Embodiment 9a wherein the        heteroaromatic ring is a 5-membered heteroaromatic ring.    -   Embodiment 9c. A compound of Embodiment 9a wherein the        heteroaromatic ring is a 5-membered heteroaromatic ring having a        nitrogen atom at the 2-position.    -   Embodiment 9d. A compound of Embodiment 9a wherein the        heteroaromatic ring is a 6-membered heteroaromatic ring.    -   Embodiment 9e. A compound of Embodiment 9a wherein the        heteroaromatic ring is a 6-membered heteroaromatic ring having a        nitrogen atom at the 2-position.    -   Embodiment 9f. A compound of Embodiment 9a wherein the        heteroaromatic ring is a 6-membered heteroaromatic ring having a        nitrogen atom at the 2-position and substituted with C₁-C₄        haloalkyl.    -   Embodiment 9g. A compound of Embodiment 9a wherein the        heteroaromatic ring is a 6-membered heteroaromatic ring having a        nitrogen atom at the 2-position and substituted with CF₃.

Embodiments of this invention, including Embodiments 1-9g above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-9g above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-9g are illustrated by:

-   -   Embodiment A. A compound of Formula 1 wherein

X¹ is —C(R²)═C(R³)— or —C(R³)═C(R²)—; and X² is O, S or NR³.

-   -   Embodiment B. A compound of Embodiment A wherein    -   Q is Q-3.    -   Embodiment C. A compound of Embodiment B wherein    -   Y³ is CR^(5b).    -   Embodiment D. A compound of Embodiment C wherein    -   A is CH or CF; and    -   m is 0.    -   Embodiment E. A compound of Embodiment D wherein    -   R² is C(═Z)NR⁶R⁷.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of (compound numbers refer to Index Tables A and B):

-   -   compound 7;    -   compound 8;    -   compound 9;    -   compound 10;    -   compound 14;    -   compound 15;    -   compound 18;    -   compound 20;    -   compound 30;    -   compound 32;    -   compound 35;    -   compound 38; and    -   compound 39.

Of note is that compounds of this invention are characterized byfavorable metabolic and/or soil residual patterns and exhibit activitycontrolling a spectrum of agronomic and nonagronomic invertebrate pests.

Of particular note, for reasons of invertebrate pest control spectrumand economic importance, protection of agronomic crops from damage orinjury caused by invertebrate pests by controlling invertebrate pestsare embodiments of the invention. Compounds of this invention because oftheir favorable translocation properties or systemicity in plants alsoprotect foliar or other plant parts which are not directly contactedwith a compound of Formula 1 or a composition comprising the compound.

Also noteworthy as embodiments of the present invention are compositionscomprising a compound of any of the preceding Embodiments, as well asany other embodiments described herein, and any combinations thereof,and at least one additional component selected from the group consistingof a surfactant, a solid diluent and a liquid diluent, said compositionsoptionally further comprising at least one additional biologicallyactive compound or agent.

Further noteworthy as embodiments of the present invention arecompositions for controlling an invertebrate pest comprising a compoundof any of the preceding Embodiments, as well as any other embodimentsdescribed herein, and any combinations thereof, and at least oneadditional component selected from the group consisting of a surfactant,a solid diluent and a liquid diluent, said compositions optionallyfurther comprising at least one additional biologically active compoundor agent. Embodiments of the invention further include methods forcontrolling an invertebrate pest comprising contacting the invertebratepest or its environment with a biologically effective amount of acompound of any of the preceding Embodiments (e.g., as a compositiondescribed herein).

Embodiments of the invention also include a composition comprising acompound of any of the preceding Embodiments, in the form of a soildrench liquid formulation. Embodiments of the invention further includemethods for controlling an invertebrate pest comprising contacting thesoil with a liquid composition as a soil drench comprising abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include a spray composition forcontrolling an invertebrate pest comprising a biologically effectiveamount of a compound of any of the preceding Embodiments and apropellant. Embodiments of the invention further include a baitcomposition for controlling an invertebrate pest comprising abiologically effective amount of a compound of any of the precedingEmbodiments, one or more food materials, optionally an attractant, andoptionally a humectant. Embodiments of the invention also include adevice for controlling an invertebrate pest comprising said baitcomposition and a housing adapted to receive said bait composition,wherein the housing has at least one opening sized to permit theinvertebrate pest to pass through the opening so the invertebrate pestcan gain access to said bait composition from a location outside thehousing, and wherein the housing is further adapted to be placed in ornear a locus of potential or known activity for the invertebrate pest.

Embodiments of the invention also include methods for protecting a seedfrom an invertebrate pest comprising contacting the seed with abiologically effective amount of a compound of any of the precedingEmbodiments.

Embodiments of the invention also include methods for protecting ananimal from an invertebrate parasitic pest comprising administering tothe animal a parasiticidally effective amount of a compound of any ofthe preceding Embodiments.

Embodiments of the invention also include methods for controlling aninvertebrate pest comprising contacting the invertebrate pest or itsenvironment with a biologically effective amount of a compound ofFormula 1, an N-oxide or a salt thereof, (e.g., as a compositiondescribed herein), provided that the methods are not methods of medicaltreatment of a human or animal body by therapy.

This invention also relates to such methods wherein the invertebratepest or its environment is contacted with a composition comprising abiologically effective amount of a compound of Formula 1, an N-oxide ora salt thereof, and at least one additional component selected from thegroup consisting of surfactants, solid diluents and liquid diluents,said composition optionally further comprising a biologically effectiveamount of at least one additional biologically active compound or agent,provided that the methods are not methods of medical treatment of ahuman or animal body by therapy.

The compounds of Formula 1 can be prepared by one or more of thefollowing methods and variations as described in Schemes 1-12. Thedefinitions of substituents in the compounds of Formulae 1-22 below areas defined above in the Summary of the Invention unless otherwise noted.Compounds of Formulae 1a-1f are various subsets of the compounds ofFormula 1, and all substituents for Formulae 1a-1f are as defined abovefor Formula 1. The following abbreviations are used: THF istetrahydrofuran, DMF is N,N-dimethylformamide, NMP isN-methylpyrrolidinone, Ac is acetate, MS is mesylate, Tf is triflate,and Nf is nonaflate.

Compounds of Formula 1a (Formula 1 wherein Q is Q-1, Q-3 or Q-4) can beprepared as shown in Scheme 1 by the coupling of a heterocyclic compoundof Formula 2 (wherein LG is a suitable leaving group such as Cl, Br, I,Tf or NO with a heterocyclic compound of Formula 3 (wherein M is asuitable metal or metalloid such as a Mg, Zn or B species) in thepresence of a catalyst and appropriate ligand. Catalysts can begenerated from transition metals such as Pd (for example Pd(OAc)₂ orPd₂(dba)₃ and mono- or bi-dentate ligands such as PPh₃, PCy₃, Pt-Bu₃,x-phos, xantphos, s-phos, and dppf. Typical bases used includecarbonates such as sodium carbonate or cesium carbonate, phosphates suchas potassium triphosphate, amines such as ethyldiisopropylamine, oralkoxides such as sodium tert-butoxide. Typical solvents include THF,dioxane, toluene, ethanol, DMF, water or mixtures thereof. Typicalreaction temperatures range from ambient temperature to the boilingpoint of the solvent.

Compounds of Formula 1a (Formula 1 wherein Q is Q-1, Q-3 or Q-4) canalso be prepared as shown in Scheme 2 by the coupling of a compound ofFormula 4 with a compound of Formula 5 (wherein LG is a suitable leavinggroup such as Cl, Br, I, Tf or Nf) in the presence of a catalyst and anappropriate ligand. A variety of catalysts can be used in the method ofScheme 2, and these can be generated from a transition metal speciessuch as copper or Pd (for example complexes such as Pd(OAc)₂ orPd₂(dba)₃) and a ligand. Typical ligands may be mono- or bi-dentate, andinclude PPh₃, PCy₃, Pt-Bu₃, x-phos, xantphos, s-phos, and dppf. Typicalbases used include carbonates such as sodium carbonate or cesiumcarbonate, phosphates such as potassium triphosphate, amines such asethyldiisopropylamine or alkoxides such as sodium tert-butoxide.Additives such as molecular sieves, Bu₄N⁺Br⁻ or copper or silver salts(e.g., AgOAc) can be beneficial. Typical reaction solvents include THF,dioxane, toluene, ethanol, DMF, water, or mixtures thereof. Typicalreaction temperatures range from ambient temperature to the boilingpoint of the solvent. For examples, see Chemical Communications 2011,47(17), pages 5043-5045; Journal of the American Chemical Society 2010,132(11), pages 3674-3675; Heterocycles 2011, 83(6), pages 1371-1376;U.S. Patent Application Publication 20090076266; Bulletin of theChemical Society of Japan 1998, 71(2), pages 467-473; TetrahedronLetters 2008, 49(10), pages 1598-1600; and Tetrahedron Letters 2010,51(42), pages 5624-5627.

Compounds of Formula 2 wherein LG is halogen can be prepared from thecorresponding amines by treatment with a source of ON⁺ such as isoamylnitrite or t-butyl nitrite or nitrous acid in the presence of a halogensource such as CuBr₂ or BnNEt₃ ⁺Br⁻. Preferred reaction conditionsinclude aqueous or organic solvents such as THF or acetonitrile, andreaction temperatures ranging from 0° C. to the boiling point of thesolvent.

Compounds of Formula 2 wherein LG is Cl or Br can also be prepared fromthe corresponding hydroxy compounds by treatment with a halogenatingagent such as POCl₃, PCl₅, PBr₃ or SOCl₂. Compounds of Formula 2 whereinLG is OMS or OTf can also be prepared from the corresponding hydroxycompounds by treatment with MsCl or Tf₂O.

Compounds of Formula 4 can be prepared from the corresponding aminecompounds by treatment with a source of ON⁺ such as isoamyl nitrite ort-butyl nitrite. Preferred reaction conditions include ethereal solventssuch as THF at temperatures ranging from ambient temperature to theboiling point of the solvent.

Compounds of Formula 6 can be prepared by electrophilic halogenation ofthe corresponding compounds of Formula 7 by treatment with ahalogenating agent such as N-bromosuccinimide in a suitable solvent suchas DMF, NMP or acetic acid at temperatures ranging from ambienttemperature up to the boiling point of the solvent (Scheme 3).

Compounds of Formula 8 can be prepared from ortho-unsubstituted anilinesof Formula 9 and a thiocyanate anion (wherein M is K⁺, Na⁺ or Bu₄N⁺⁾ asshown in Scheme 4. The reaction can be conducted in a single step inacetic acid for example, or through the intermediacy of a thio-ureafollowed by oxidation. Suitable oxidants include bromine.

Compounds of Formula 1c can be prepared from compounds of Formula 11 bythe method shown in Scheme 6 via oxidation of a compound of Formula 11with molecular oxygen or a peroxide such as t-butyl hydroperoxide in thepresence of a copper (II) catalyst such as Cu(OAc)₂ or CuBr₂. Typicalreaction conditions included alcoholic solvents such as t-amyl alcohol,DMF, NMP or aqueous ammonia, and reaction temperatures from 60° C. tothe boiling point of the solvent.

2-Aminoazo compounds of Formula 11 can be prepared by reaction of ananiline of Formula 9 with a diazonium salt of Formula 12 by methodsknown in the art (see, for example, March, J., Advanced OrganicChemistry, Wiley, 1992, pages 525-526). Compounds of Formula 11 can alsobe prepared by reaction of an aryl nitroso compound of Formula 13 with adiamine of Formula 14 in a solvent such as acetic acid. These twomethods are shown in Scheme 7.

Compounds of Formula 1d can be prepared by condensation of a compound ofFormula 14 (wherein Lg is a suitable leaving group such as Cl or Br)with an amine of Formula 15 as shown in Scheme 8. Typical reactionconditions include an alcoholic solvent such as ethanol or toluene, anda reaction temperature range from ambient temperature to the boilingpoint of the solvent. The pyridine nitrogen can optionally be protectedas a BH₃ adduct, an N-oxide, or a 2- or 6-halopyridine derivative.

Compounds of Formula 1e can be prepared as shown in Scheme 9 by thecycloaddition of 2-aminopyridines of Formula 15 with arylnitriles ofFormula 16 (see, for example, Journal of the American Chemical Society2009, 131(42), pages 15080-15081, and WO 2013041472.

Compounds of Formula 1e can also be prepared by rearrangement ofcompounds of Formula 17 by treatment with base as shown in Scheme 10(see, for example, J. Het Chem 1970, 7 page 1019). Compounds of Formula17 can be prepared by methods described in WO 2008006540 and J. Org.Chem., 1966, page 251.

Intermediates of Formula 18 can be prepared by the method shown inScheme 11 by treatment of a 2-aminopyridine of Formula 15 with anisocyanate followed by hydroxylamine and a suitable base such astriethylamine.

Compounds of Formula 1 wherein Q is Q-4 can also be prepared by themethod described in Synthesis Example 1.

Compounds of Formula 1f can be prepared as shown in Scheme 12 byoxidative cyclization of an aryl aldehyde of Formula 20 with an anilineof Formula 19 bearing an ortho-halogen, preferably iodine, in thepresence of sulfur which acts as both a source of sulfur and as anoxidizing agent. The reaction is carried out in the presence of a basesuch as K₂CO₃ in a suitable solvent such as water or DMF, and iscatalyzed by the addition of copper salts (for example, CuI or CuCl₂)and preferably a suitable ligand such as 1,10-phenanthroline. Typicalreaction temperatures range from 70° C. to the boiling point of thesolvent.

Compounds of Formula 1f can also be prepared by cyclization of2-halothioamides of Formula 21 as shown in the second reaction of Scheme12 with a base such as KOtBu, NaH, DBU or Cs₂CO₃ in a suitable solventsuch as toluene or DMF, optionally with the addition of copper saltssuch as CuI, and preferably a suitable ligand such as1,10-phenanthroline. This reaction can also be catalyzed by Pd speciessuch as that prepared from Pd₂(dba)₃ and (t-Bu)₂P-o-biphenyl, a basesuch as Cs₂CO₃ in a suitable solvent, such as 1,2-dimethoxyethane ordioxane. Typical reaction temperatures range from 80° C. to the boilingpoint of the solvent. For copper- and Pd-catalyzed reactions, thehalogen substituent on the compound of Formula 21 is preferably Br or I.For example, see Journal of Organic Chemistry 2006, 71(5), pages1802-1808; Tetrahedron Letters 2003, 44(32), pages 6073-6077; SyntheticCommunications 1991, 21(5), pages 625-33; and Eur. Pat. Appl. No.450420.

Compounds of Formula 1f can also be prepared by the oxidativecyclization of thioamides of Formula 22 as shown in the third reactionof Scheme 12. Oxidants typically used in this method include bromine oriodine, DDQ and K₃Fe(CN)₆. For example, see Tetrahedron 2007, 63(41),pages 10276-10281; Synthesis 2007, (6), 819-823; and U.S. Pat. Appl.Publ., 20120215154.

Compounds of Formula 1, and intermediates used in the preparation ofcompounds of Formula 1, wherein Z is S can be prepared by thionation ofthe corresponding compounds wherein Z is O with, for example, Lawesson'sreagent (CAS No. 19172-47-5), Belleau's reagent (CAS No. 88816-02-8) orP₂S₅. The thionation reactions are typically conducted in solvents suchas toluene, xylenes or dioxane, and at elevated temperature from 80° C.to the boiling point of the solvent.

It is recognized that some reagents and reaction conditions describedabove for preparing compounds of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after introduction of the reagentsdepicted in the individual schemes, additional routine synthetic stepsnot described in detail may be needed to complete the synthesis ofcompounds of Formula 1. One skilled in the art will also recognize thatit may be necessary to perform a combination of the steps illustrated inthe above schemes in an order other than that implied by the particularsequence presented to prepare the compounds of Formula 1.

One skilled in the art will also recognize that compounds of Formula 1and the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Synthesis Examples are, therefore, to beconstrued as merely illustrative, and not limiting of the disclosure inany way whatsoever. Steps in the following Synthesis Examples illustratea procedure for each step in an overall synthetic transformation, andthe starting material for each step may not have necessarily beenprepared by a particular preparative run whose procedure is described inother Examples or Steps. Percentages are by weight except forchromatographic solvent mixtures or where otherwise indicated. Parts andpercentages for chromatographic solvent mixtures are by volume unlessotherwise indicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane; “s” means singlet, “d” means doublet, “t” meanstriplet, “q” means quartet, “m” means multiplet, “dd” means doublet ofdoublets, “dt” means doublet of triplets, “br s” means broad singlet.DMF means N,N-dimethylformamide. Compound numbers refer to Index TablesA and B.

Synthesis Example 1 Preparation of6-(3-pyridinyl)-N-[1-(2,2,2-trifluoroethyl)]imidazo[2,1-b]thiazole-3-carboxamide(Compound 2) Step A: Preparation of6-(3-pyridinyl)imidazo[2,1-b]thiazole-3-carboxylic acid ethyl ester

To a mixture of ethyl 2-aminothiazole-4-carboxylate (4.6 g, 24.7 mmol)and 3-(bromoacetyl)pyridine hydrogen bromide salt (6.74 g, 24 mmol) inmethyl ethyl ketone (150 mL) at 80° C. was added solid potassiumcarbonate (9.93 g, 72 mmol). The resulting reaction mixture was heatedto reflux for 9 hours and then cooled to room temperature. Three moreidentical reactions were run under the same reaction conditions and onthe same scale. All four reaction mixtures were then combined,concentrated, and saturated aqueous sodium bicarbonate solution (200 mL)and dichloromethane (200 mL) were added to the resulting residue. Theaqueous phase was extracted with dichloromethane (5×30 mL), the combinedorganic phases were concentrated, and the crude product was purified bycolumn chromatography (silica gel eluted with ethyl acetate) to providethe title compound.

Step B: Preparation of6-(3-pyridinyl)-N-[1-(2,2,2-trifluoroethyl)]imidazo[2,1-b]thiazole-3-carboxamide

A mixture of the ester prepared in Step A (0.34 g, 1.24 mmol) andaqueous NaOH (1 N, 3.7 mL, 3.7 mmol) was stirred in methanol (10 mL) for12 hours. The reaction mixture was then concentrated under reducedpressure to remove methanol, and the resulting aqueous solution wasneutralized with 1 N HCl to pH 6 to precipitate the carboxylic acid. Thesolid carboxylic acid was isolated by filtration, dried, and useddirectly in the next step without further purification.

A mixture of the carboxylic acid prepared above (0.04 g, 0.16 mmol),2,2,2-trifluoroethylamine (0.5 mL),1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium3-oxide hexafluorophosphate(1-) (1:1) (0.068 g, 0.18 mmol), andtriethylamine (0.07 mL, 5.2 mmol) in DMF (3 mL) was stirred at roomtemperature for 12 hours. The reaction mixture was then concentratedunder vacuum to remove DMF, and the residue was purified by MPLC columnchromatography (silica gel eluted with ethyl acetate, methanol, andtriethylamine in a ratio of 8:1:1) to obtain the title compound (52.7mg), a compound of this invention.

Specific compounds of Formula 1, prepared by the methods and variationsas described in preceding Schemes 1-12 and Synthesis Example 1, areshown in the following Index Tables.

Abbreviations used in the Index Tables may include: Cmpd means Compound,Me is methyl, Et is ethyl, and Pr is propyl.

INDEX TABLE A

Cmpd. Mass Spec No. R A Data 1 —C(O)NHNHC(O)OMe CH 318.1 2 —C(O)NHCH₂CF₃CH 327.2 3 —C(O)NHN(Et)C(O)OMe CH 346.3 4 —C(O)NHCH₂(2-pyrimidinyl) CH337.2 5 —C(O)NH₂ CH 245.3 6 —C(O)NHC(CN)Me₂ CH 312.2 7 —C(O)NHC(Me)₂CNCF 330 8 —C(O)NHC(Me)₂CO₂Me CF 363 9 —C(O)NHCH₂CH₂CF₃ CF 358.9 10—C(O)NHCH(i-Pr)CO₂Me CF 377 11 —C(O)NHCH₂CF₃ N 328 12—C(O)NH(cyclopropyl) N 283 13 —C(O)NHC(Me)₂CONHMe CF 362 14—C(O)NHC(Me)₂CONMe₂ CF 376 15 —C(O)NHC(Me)₂CONHEt CF 376 16—C(O)NH(i-Pr) CF 305 17 —C(O)NHC(Me)₂COOH CF 349 18—C(O)NHCH(i-Pr)CONHMe CF 376 19 —C(O)NHCH(i-Pr)CONMe₂ CF 390 20—C(O)NHCH(i-Pr)CONHEt CF 390 21 —C(O)NHC(Me)₂CN N 313 22—C(O)NHCH₂CH₂CF₃ N 342 23 —C(O)NHCH(i-Pr)CONHEt N 373 24—C(O)NHC(Me)₂CONHMe N 345 25 —C(O)NHC(Me)₂CONHEt N 359 26—C(O)NH(cyclopropyl) N 288 27 —C(O)NHCH(Me)CH₂OMe N 318 28—C(O)NHCH(i-Pr)CONHMe N 359 29 —C(O)NHCH(i-Pr)CONMe₂ N 373 30—C(O)NHC(Me)₂CO₂Me N 346 31 —OC(O)NHCH(i-Pr)CO₂Me N 360 32—C(O)NHC(Me)₂CONMe₂ N 359

INDEX TABLE B

Cmpd. Mass Spec No. R A Data 33 —C(O)NHCH₂CF₃ CH 327 34—C(O)NHCH₂(2-pyrimidinyl) CH 337 35 —C(O)NHCH₂CF₃ CF 345 36—C(O)NHCH₂(tetrahydro-2-furanyl) CH 329 37—C(O)NHCH₂(5-methyl-2-pyrazinyl) CH 351 38 —C(O)NH(cyclopropyl) CF 30339 —C(O)NHCH(Me)CH₂OMe CF 335 40 —C(O)NHCH₂CF₃ N 328 41 —C(O)NHNHCO₂Me N319 42 —C(O)NHCH₂(2-pyrimidinyl) N 338 43—C(O)NHCH₂(5-methyl-2-pyrazinyl) N 352 44—C(O)NHCH₂(tetrahydro-2-furanyl) N 330 45 —C(O)NHNHCO₂Me CH 318 46—C(O)NHCH₂(5-methyl-2-pyrazinyl) CF 369 47 —C(O)NHNHCO₂Me CF 336 48—C(O)NHCH₂(2-pyrimidinyl) CF 355 49 —C(O)NHCH₂(tetrahydro-2-furanyl) CF347

A compound of this invention will generally be used as an invertebratepest control active ingredient in a composition, i.e. formulation, withat least one additional component selected from the group consisting ofsurfactants, solid diluents and liquid diluents, which serves as acarrier. The formulation or composition ingredients are selected to beconsistent with the physical properties of the active ingredient, modeof application and environmental factors such as soil type, moisture andtemperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions, oil in wateremulsions, flowable concentrates and/or suspoemulsions) and the like,which optionally can be thickened into gels. The general types ofaqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsion,oil in water emulsion, flowable concentrate and suspoemulsion. Thegeneral types of nonaqueous liquid compositions are emulsifiableconcentrate, microemulsifiable concentrate, dispersible concentrate andoil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water, but occasionallyanother suitable medium like an aromatic or paraffinic hydrocarbon orvegetable oil. Spray volumes can range from about one to severalthousand liters per hectare, but more typically are in the range fromabout ten to several hundred liters per hectare. Sprayable formulationscan be tank mixed with water or another suitable medium for foliartreatment by aerial or ground application, or for application to thegrowing medium of the plant. Liquid and dry formulations can be metereddirectly into drip irrigation systems or metered into the furrow duringplanting. Liquid and solid formulations can be applied onto seeds ofcrops and other desirable vegetation as seed treatments before plantingto protect developing roots and other subterranean plant parts and/orfoliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water- 0.001-90 0-99.999 0-15 soluble Granules, Tablets and PowdersOil Dispersions, Suspensions,    1-50 40-99    0-50 Emulsions, Solutions(including Emulsifiable Concentrates) Dusts    1-25 70-99    0-5 Granules and Pellets 0.001-99 5-99.999 0-15 High Strength Compositions  90-99 0-10    0-2 

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates(e.g., triethylphosphate), ethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, polypropylene glycol, propylenecarbonate, butylene carbonate, paraffins (e.g., white mineral oils,normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes,glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons,dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones suchas cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters alkyl and aryl benzoates, γ-butyrolactone, and alcohols,which can be linear, branched, saturated or unsaturated, such asmethanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutylalcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecylalcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecylalcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol,diacetone alcohol, cresol and benzyl alcohol. Liquid diluents alsoinclude glycerol esters of saturated and unsaturated fatty acids(typically C₆-C₂₂), such as plant seed and fruit oils (e.g., oils ofolive, castor, linseed, sesame, corn (maize), peanut, sunflower,grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palmkernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, codliver oil, fish oil), and mixtures thereof. Liquid diluents also includealkylated fatty acids (e.g., methylated, ethylated, butylated) whereinthe fatty acids may be obtained by hydrolysis of glycerol esters fromplant and animal sources, and can be purified by distillation. Typicalliquid diluents are described in Marsden, Solvents Guide, 2nd Ed.,Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 μmrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. Nos.4,144,050, 3,920,442 and DE 3,246,493. Tablets can be prepared as taughtin U.S. Pat. Nos. 5,180,587, 5,232,701 and 5,208,030. Films can beprepared as taught in GB 2,095,558 and U.S. Pat. No. 3,299,566.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all formulations are prepared in conventionalways. Compound numbers refer to compounds in Index Tables A-B. Withoutfurther elaboration, it is believed that one skilled in the art usingthe preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Percentages are by weight except where otherwise indicated.

Example A

High Strength Concentrate

Compound 7 98.5% silica aerogel 0.5% synthetic amorphous fine silica1.0%

Example B

Wettable Powder

Compound 8 65.0% dodecylphenol polyethylene glycol ether 2.0% sodiumligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite(calcined) 23.0%

Example C

Granule

Compound 9 10.0% attapulgite granules (low volatile matter, 0.71/0.30mm; 90.0% U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet

Compound 10 25.0% anhydrous sodium sulfate 10.0% crude calciumligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0%calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate

Compound 14 10.0% polyoxyethylene sorbitol hexoleate 20.0% C₆-C₁₀ fattyacid methyl ester 70.0%

Example F

Microemulsion

Compound 15 5.0% polyvinylpyrrolidone-vinyl acetate copolymer 30.0%alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water 20.0%

Example G

Seed Treatment

Compound 18 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00%montan acid wax 5.00% calcium ligninsulfonate 1.00%polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol(POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water65.75%

Example H

Fertilizer Stick

Compound 20 2.5% pyrrolidone-styrene copolymer 4.8% tristyrylphenyl16-ethoxylate 2.3% talc 0.8% corn starch 5.0% slow-release fertilizer36.0% kaolin 38.0% water 10.6%

Example I

Suspension Concentrate

compound 30  35% butyl polyoxyethylene/polypropylene block copolymer4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylicpolymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone baseddefoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% water 53.7% 

Example J

Emulsion in Water

compound 32 10.0%  butyl polyoxyethylene/polypropylene block copolymer4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylicpolymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone baseddefoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromatic petroleum basedhydrocarbon 20.0 water 58.7% 

Example K

Oil Dispersion

compound 35 25% polyoxyethylene sorbitol hexaoleate 15% organicallymodified bentonite clay 2.5%  fatty acid methyl ester 57.5% 

Example L

Suspoemulsion

compound 38 10.0% imidacloprid 5.0% butyl polyoxyethylene/polypropyleneblock copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromaticpetroleum based hydrocarbon 20.0% water 53.7%

Compounds of this invention exhibit activity against a wide spectrum ofinvertebrate pests. These pests include invertebrates inhabiting avariety of environments such as, for example, plant foliage, roots,soil, harvested crops or other foodstuffs, building structures or animalinteguments. These pests include, for example, invertebrates feeding onfoliage (including leaves, stems, flowers and fruits), seeds, wood,textile fibers or animal blood or tissues, and thereby causing injury ordamage to, for example, growing or stored agronomic crops, forests,greenhouse crops, ornamentals, nursery crops, stored foodstuffs or fiberproducts, or houses or other structures or their contents, or beingharmful to animal health or public health. Those skilled in the art willappreciate that not all compounds are equally effective against allgrowth stages of all pests.

These present compounds and compositions are thus useful agronomicallyfor protecting field crops from phytophagous invertebrate pests, andalso nonagronomically for protecting other horticultural crops andplants from phytophagous invertebrate pests. This utility includesprotecting crops and other plants (i.e. both agronomic and nonagronomic)that contain genetic material introduced by genetic engineering (i.e.transgenic) or modified by mutagenesis to provide advantageous traits.Examples of such traits include tolerance to herbicides, resistance tophytophagous pests (e.g., insects, mites, aphids, spiders, nematodes,snails, plant-pathogenic fungi, bacteria and viruses), improved plantgrowth, increased tolerance of adverse growing conditions such as highor low temperatures, low or high soil moisture, and high salinity,increased flowering or fruiting, greater harvest yields, more rapidmaturation, higher quality and/or nutritional value of the harvestedproduct, or improved storage or process properties of the harvestedproducts. Transgenic plants can be modified to express multiple traits.Examples of plants containing traits provided by genetic engineering ormutagenesis include varieties of corn, cotton, soybean and potatoexpressing an insecticidal Bacillus thuringiensis toxin such as YIELDGARD®, KNOCKOUT®, STARLINK®, BOLLGARD®, NuCOTN® and NEWLEAF®, INVICTARR2 PRO™, and herbicide-tolerant varieties of corn, cotton, soybean andrapeseed such as ROUNDUP READY®, LIBERTY LINK®, IMI®, STS® andCLEARFIELD®, as well as crops expressing N-acetyltransferase (GAT) toprovide resistance to glyphosate herbicide, or crops containing the HRAgene providing resistance to herbicides inhibiting acetolactate synthase(ALS). The present compounds and compositions may interactsynergistically with traits introduced by genetic engineering ormodified by mutagenesis, thus enhancing phenotypic expression oreffectiveness of the traits or increasing the invertebrate pest controleffectiveness of the present compounds and compositions. In particular,the present compounds and compositions may interact synergistically withthe phenotypic expression of proteins or other natural products toxic toinvertebrate pests to provide greater-than-additive control of thesepests.

Compositions of this invention can also optionally comprise plantnutrients, e.g., a fertilizer composition comprising at least one plantnutrient selected from nitrogen, phosphorus, potassium, sulfur, calcium,magnesium, iron, copper, boron, manganese, zinc, and molybdenum. Of noteare compositions comprising at least one fertilizer compositioncomprising at least one plant nutrient selected from nitrogen,phosphorus, potassium, sulfur, calcium and magnesium. Compositions ofthe present invention which further comprise at least one plant nutrientcan be in the form of liquids or solids. Of note are solid formulationsin the form of granules, small sticks or tablets. Solid formulationscomprising a fertilizer composition can be prepared by mixing thecompound or composition of the present invention with the fertilizercomposition together with formulating ingredients and then preparing theformulation by methods such as granulation or extrusion. Alternativelysolid formulations can be prepared by spraying a solution or suspensionof a compound or composition of the present invention in a volatilesolvent onto a previous prepared fertilizer composition in the form ofdimensionally stable mixtures, e.g., granules, small sticks or tablets,and then evaporating the solvent.

Nonagronomic uses refer to invertebrate pest control in the areas otherthan fields of crop plants. Nonagronomic uses of the present compoundsand compositions include control of invertebrate pests in stored grains,beans and other foodstuffs, and in textiles such as clothing andcarpets. Nonagronomic uses of the present compounds and compositionsalso include invertebrate pest control in ornamental plants, forests, inyards, along roadsides and railroad rights of way, and on turf such aslawns, golf courses and pastures. Nonagronomic uses of the presentcompounds and compositions also include invertebrate pest control inhouses and other buildings which may be occupied by humans and/orcompanion, farm, ranch, zoo or other animals. Nonagronomic uses of thepresent compounds and compositions also include the control of pestssuch as termites that can damage wood or other structural materials usedin buildings.

Nonagronomic uses of the present compounds and compositions also includeprotecting human and animal health by controlling invertebrate peststhat are parasitic or transmit infectious diseases. The controlling ofanimal parasites includes controlling external parasites that areparasitic to the surface of the body of the host animal (e.g.,shoulders, armpits, abdomen, inner part of the thighs) and internalparasites that are parasitic to the inside of the body of the hostanimal (e.g., stomach, intestine, lung, veins, under the skin, lymphatictissue). External parasitic or disease transmitting pests include, forexample, chiggers, ticks, lice, mosquitoes, flies, mites and fleas.Internal parasites include heartworms, hookworms and helminths.Compounds and compositions of the present invention are suitable forsystemic and/or non-systemic control of infestation or infection byparasites on animals. Compounds and compositions of the presentinvention are particularly suitable for combating external parasitic ordisease transmitting pests. Compounds and compositions of the presentinvention are suitable for combating parasites that infest agriculturalworking animals, such as cattle, sheep, goats, horses, pigs, donkeys,camels, buffalos, rabbits, hens, turkeys, ducks, geese and bees; petanimals and domestic animals such as dogs, cats, pet birds and aquariumfish; as well as so-called experimental animals, such as hamsters,guinea pigs, rats and mice. By combating these parasites, fatalities andperformance reduction (in terms of meat, milk, wool, skins, eggs, honey,etc.) are reduced, so that applying a composition comprising a compoundof the present invention allows more economic and simple husbandry ofanimals.

Examples of agronomic or nonagronomic invertebrate pests include eggs,larvae and adults of the order Lepidoptera, such as armyworms, cutworms,loopers, and heliothines in the family Noctuidae (e.g., pink stem borer(Sesamia inferens Walker), corn stalk borer (Sesamia nonagrioidesLefebvre), southern armyworm (Spodoptera eridania Cramer), fall armyworm(Spodoptera frugiperda J. E. Smith), beet armyworm (Spodoptera exiguaHübner), cotton leafworm (Spodoptera littoralis Boisduval),yellowstriped armyworm (Spodoptera ornithogalli Guenée), black cutworm(Agrotis ipsilon Hufnagel), velvetbean caterpillar (Anticarsiagemmatalis Hübner), green fruitworm (Lithophane antennata Walker),cabbage armyworm (Barathra brassicae Linnaeus), soybean looper(Pseudoplusia includens Walker), cabbage looper (Trichoplusia niHübner), tobacco budworm (Heliothis virescens Fabricius)); borers,casebearers, webworms, coneworms, cabbageworms and skeletonizers fromthe family Pyralidae (e.g., European corn borer (Ostrinia nubilalisHübner), navel orangeworm (Amyelois transitella Walker), corn rootwebworm (Crambus caliginosellus Clemens), sod webworms (Pyralidae:Crambinae) such as sod worm (Herpetogramma licarsisalis Walker),sugarcane stem borer (Chilo infuscatellus Snellen), tomato small borer(Neoleucinodes elegantalis Guenée), green leafroller (Cnaphalocrocismedinalis), grape leaffolder (Desmia funeralis Hübner), melon worm(Diaphania nitidalis Stoll), cabbage center grub (Helluala hydralisGuenée), yellow stem borer (Scirpophaga incertulas Walker), early shootborer (Scirpophaga infuscatellus Snellen), white stem borer (Scirpophagainnotata Walker), top shoot borer (Scirpophaga nivella Fabricius),dark-headed rice borer (Chilo polychrysus Meyrick), striped riceborer(Chilo suppressalis Walker), cabbage cluster caterpillar (Crocidolomiabinotalis English)); leafrollers, budworms, seed worms, and fruit wormsin the family Tortricidae (e.g., codling moth (Cydia pomonellaLinnaeus), grape berry moth (Endopiza viteana Clemens), oriental fruitmoth (Grapholita molesta Busck), citrus false codling moth(Cryptophlebia leucotreta Meyrick), citrus borer (Ecdytolopha aurantianaLima), redbanded leafroller (Argyrotaenia velutinana Walker),obliquebanded leafroller (Choristoneura rosaceana Harris), light brownapple moth (Epiphyas postvittana Walker), European grape berry moth(Eupoecilia ambiguella Hübner), apple bud moth (Pandemis pyrusanaKearfott), omnivorous leafroller (Platynota stultana Walsingham), barredfruit-tree tortrix (Pandemis cerasana Hübner), apple brown tortrix(Pandemis heparana Denis & Schiffermuller)); and many other economicallyimportant lepidoptera (e.g., diamondback moth (Plutella xylostellaLinnaeus), pink bollworm (Pectinophora gossypiella Saunders), gypsy moth(Lymantria dispar Linnaeus), peach fruit borer (Carposina niponensisWalsingham), peach twig borer (Anarsia lineatella Zeller), potatotuberworm (Phthorimaea operculella Zeller), spotted teniform leafminer(Lithocolletis blancardella Fabricius), Asiatic apple leafminer(Lithocolletis ringoniella Matsumura), rice leaffolder (Lerodea eufalaEdwards), apple leafminer (Leucoptera scitella Zeller)); eggs, nymphsand adults of the order Blattodea including cockroaches from thefamilies Blattellidae and Blattidae (e.g., oriental cockroach (Blattaorientalis Linnaeus), Asian cockroach (Blatella asahinai Mizukubo),German cockroach (Blattella germanica Linnaeus), brownbanded cockroach(Supella longipalpa Fabricius), American cockroach (Periplanetaamericana Linnaeus), brown cockroach (Periplaneta brunnea Burmeister),Madeira cockroach (Leucophaea maderae Fabricius)), smoky brown cockroach(Periplaneta fuliginosa Service), Australian Cockroach (Periplanetaaustralasiae Fabr.), lobster cockroach (Nauphoeta cinerea Olivier) andsmooth cockroach (Symploce pallens Stephens)); eggs, foliar feeding,fruit feeding, root feeding, seed feeding and vesicular tissue feedinglarvae and adults of the order Coleoptera including weevils from thefamilies Anthribidae, Bruchidae, and Curculionidae (e.g., boll weevil(Anthonomus grandis Boheman), rice water weevil (Lissorhoptrusoryzophilus Kuschel), granary weevil (Sitophilus granarius Linnaeus),rice weevil (Sitophilus oryzae Linnaeus)), annual bluegrass weevil(Listronotus maculicollis Dietz), bluegrass billbug (Sphenophorusparvulus Gyllenhal), hunting billbug (Sphenophorus venatus vestitus),Denver billbug (Sphenophorus cicatristriatus Fahraeus)); flea beetles,cucumber beetles, rootworms, leaf beetles, potato beetles, andleafminers in the family Chrysomelidae (e.g., Colorado potato beetle(Leptinotarsa decemlineata Say), western corn rootworm (Diabroticavirgifera LeConte)); chafers and other beetles from the familyScarabaeidae (e.g., Japanese beetle (Popillia japonica Newman), orientalbeetle (Anomala orientalis Waterhouse, Exomala orientalis (Waterhouse)Baraud), northern masked chafer (Cyclocephala borealis Arrow), southernmasked chafer (Cyclocephala immaculata Olivier or C. lurida Bland), dungbeetle and white grub (Aphodius spp.), black turfgrass ataenius(Ataenius spretulus Haldeman), green June beetle (Cotinis nitidaLinnaeus), Asiatic garden beetle (Maladera castanea Arrow), May/Junebeetles (Phyllophaga spp.) and European chafer (Rhizotrogus majalisRazoumowsky)); carpet beetles from the family Dermestidae; wirewormsfrom the family Elateridae; bark beetles from the family Scolytidae andflour beetles from the family Tenebrionidae.

In addition, agronomic and nonagronomic pests include: eggs, adults andlarvae of the order Dermaptera including earwigs from the familyForficulidae (e.g., European earwig (Forficula auricularia Linnaeus),black earwig (Chelisoches morio Fabricius)); eggs, immatures, adults andnymphs of the orders Hemiptera and Homoptera such as, plant bugs fromthe family Miridae, cicadas from the family Cicadidae, leafhoppers (e.g.Empoasca spp.) from the family Cicadellidae, bed bugs (e.g., Cimexlectularius Linnaeus) from the family Cimicidae, planthoppers from thefamilies Fulgoroidae and Delphacidae, treehoppers from the familyMembracidae, psyllids from the family Psyllidae, whiteflies from thefamily Aleyrodidae, aphids from the family Aphididae, phylloxera fromthe family Phylloxeridae, mealybugs from the family Pseudococcidae,scales from the families Coccidae, Diaspididae and Margarodidae, lacebugs from the family Tingidae, stink bugs from the family Pentatomidae,chinch bugs (e.g., hairy chinch bug (Blissus leucopterus hirtusMontandon) and southern chinch bug (Blissus insularis Barber)) and otherseed bugs from the family Lygaeidae, spittlebugs from the familyCercopidae squash bugs from the family Coreidae, and red bugs and cottonstainers from the family Pyrrhocoridae.

Agronomic and nonagronomic pests also include: eggs, larvae, nymphs andadults of the order Acari (mites) such as spider mites and red mites inthe family Tetranychidae (e.g., European red mite (Panonychus ulmiKoch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite(Tetranychus mcdanieli McGregor)); flat mites in the familyTenuipalpidae (e.g., citrus flat mite (Brevipalpus lewisi McGregor));rust and bud mites in the family Eriophyidae and other foliar feedingmites and mites important in human and animal health, i.e. dust mites inthe family Epidermoptidae, follicle mites in the family Demodicidae,grain mites in the family Glycyphagidae; ticks in the family Ixodidae,commonly known as hard ticks (e.g., deer tick (Ixodes scapularis Say),Australian paralysis tick (Ixodes holocyclus Neumann), American dog tick(Dermacentor variabilis Say), lone star tick (Amblyomma americanumLinnaeus)) and ticks in the family Argasidae, commonly known as softticks (e.g., relapsing fever tick (Ornithodoros turicata), common fowltick (Argas radiatus)); scab and itch mites in the families Psoroptidae,Pyemotidae, and Sarcoptidae; eggs, adults and immatures of the orderOrthoptera including grasshoppers, locusts and crickets (e.g., migratorygrasshoppers (e.g., Melanoplus sanguinipes Fabricius, M. differentialisThomas), American grasshoppers (e.g., Schistocerca americana Drury),desert locust (Schistocerca gregaria Forskal), migratory locust (Locustamigratoria Linnaeus), bush locust (Zonocerus spp.), house cricket(Acheta domesticus Linnaeus), mole crickets (e.g., tawny mole cricket(Scapteriscus vicinus Scudder) and southern mole cricket (Scapteriscusborellii Giglio-Tos)); eggs, adults and immatures of the order Dipteraincluding leafminers (e.g., Liriomyza spp. such as serpentine vegetableleafminer (Liriomyza sativae Blanchard)), midges, fruit flies(Tephritidae), frit flies (e.g., Oscinella frit Linnaeus), soil maggots,house flies (e.g., Musca domestica Linnaeus), lesser house flies (e.g.,Fannia canicularis Linnaeus, F. femoralis Stein), stable flies (e.g.,Stomoxys calcitrans Linnaeus), face flies, horn flies, blow flies (e.g.,Chrysomya spp., Phormia spp.), and other muscoid fly pests, horse flies(e.g., Tabanus spp.), bot flies (e.g., Gastrophilus spp., Oestrus spp.),cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.),keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes(e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g.,Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids,and other Nematocera; eggs, adults and immatures of the orderThysanoptera including onion thrips (Thrips tabaci Lindeman), flowerthrips (Frankliniella spp.), and other foliar feeding thrips; insectpests of the order Hymenoptera including ants of the Family Formicidaeincluding the Florida carpenter ant (Camponotus floridanus Buckley), redcarpenter ant (Camponotus ferrugineus Fabricius), black carpenter ant(Camponotus pennsylvanicus De Geer), white-footed ant (Technomyrmexalbipes fr. Smith), big headed ants (Pheidole sp.), ghost ant (Tapinomamelanocephalum Fabricius); Pharaoh ant (Monomorium pharaonis Linnaeus),little fire ant (Wasmannia auropunctata Roger), fire ant (Solenopsisgeminata Fabricius), red imported fire ant (Solenopsis invicta Buren),Argentine ant (Iridomyrmex humilis Mayr), crazy ant (Paratrechinalongicornis Latreille), pavement ant (Tetramorium caespitum Linnaeus),cornfield ant (Lasius alienus Forster) and odorous house ant (Tapinomasessile Say). Other Hymenoptera including bees (including carpenterbees), hornets, yellow jackets, wasps, and sawflies (Neodiprion spp.;Cephus spp.); insect pests of the order Isoptera including termites inthe Termitidae (e.g., Macrotermes sp., Odontotermes obesus Rambur),Kalotermitidae (e.g., Cryptotermes sp.), and Rhinotermitidae (e.g.,Reticulitermes sp., Coptotermes sp., Heterotermes tenuis Hagen)families, the eastern subterranean termite (Reticulitermes flavipesKollar), western subterranean termite (Reticulitermes hesperus Banks),Formosan subterranean termite (Coptotermes formosanus Shiraki), WestIndian drywood termite (Incisitermes immigrans Snyder), powder posttermite (Cryptotermes brevis Walker), drywood termite (Incisitermessnyderi Light), southeastern subterranean termite (Reticulitermesvirginicus Banks), western drywood termite (Incisitermes minor Hagen),arboreal termites such as Nasutitermes sp. and other termites ofeconomic importance; insect pests of the order Thysanura such assilverfish (Lepisma saccharina Linnaeus) and firebrat (Thermobiadomestica Packard); insect pests of the order Mallophaga and includingthe head louse (Pediculus humanus capitis De Geer), body louse(Pediculus humanus Linnaeus), chicken body louse (Menacanthus stramineusNitszch), dog biting louse (Trichodectes canis De Geer), fluff louse(Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank),short-nosed cattle louse (Haematopinus eurysternus Nitzsch), long-nosedcattle louse (Linognathus vituli Linnaeus) and other sucking and chewingparasitic lice that attack man and animals; insect pests of the orderSiphonoptera including the oriental rat flea (Xenopsylla cheopisRothschild), cat flea (Ctenocephalides felis Bouche), dog flea(Ctenocephalides canis Curtis), hen flea (Ceratophyllus gallinaeSchrank), sticktight flea (Echidnophaga gallinacea Westwood), human flea(Pulex irritans Linnaeus) and other fleas afflicting mammals and birds.Additional arthropod pests covered include: spiders in the order Araneaesuch as the brown recluse spider (Loxosceles reclusa Gertsch & Mulaik)and the black widow spider (Latrodectus mactans Fabricius), andcentipedes in the order Scutigeromorpha such as the house centipede(Scutigera coleoptrata Linnaeus).

Examples of invertebrate pests of stored grain include larger grainborer (Prostephanus truncatus), lesser grain borer (Rhyzoperthadominica), rice weevil (Stiophilus oryzae), maize weevil (Stiophiluszeamais), cowpea weevil (Callosobruchus maculatus), red flour beetle(Tribolium castaneum), granary weevil (Stiophilus granarius), Indianmeal moth (Plodia interpunctella), Mediterranean flour beetle (Ephestiakuhniella) and flat or rusty grain beetle (Cryptolestis ferrugineus).

Compounds of the present invention may have activity on members of theClasses Nematoda, Cestoda, Trematoda, and Acanthocephala includingeconomically important members of the orders Strongylida, Ascaridida,Oxyurida, Rhabditida, Spirurida, and Enoplida such as but not limited toeconomically important agricultural pests (i.e. root knot nematodes inthe genus Meloidogyne, lesion nematodes in the genus Pratylenchus,stubby root nematodes in the genus Trichodorus, etc.) and animal andhuman health pests (i.e. all economically important flukes, tapeworms,and roundworms, such as Strongylus vulgaris in horses, Toxocara canis indogs, Haemonchus contortus in sheep, Dirofilaria immitis Leidy in dogs,Anoplocephala perfoliata in horses, Fasciola hepatica Linnaeus inruminants, etc.).

Compounds of the invention may have activity against pests in the orderLepidoptera (e.g., Alabama argillacea Huibner (cotton leaf worm),Archips argyrospila Walker (fruit tree leaf roller), A. rosana Linnaeus(European leaf roller) and other Archips species, Chilo suppressalisWalker (rice stem borer), Cnaphalocrosis medinalis Guenée (rice leafroller), Crambus caliginosellus Clemens (corn root webworm), Crambusteterrellus Zincken (bluegrass webworm), Cydiapomonella Linnaeus(codling moth), Earias insulana Boisduval (spiny bollworm), Eariasvittella Fabricius (spotted bollworm), Helicoverpa armigera Hübner(American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothisvirescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker(sod webworm), Lobesia botrana Denis & Schiffermuller (grape berrymoth), Pectinophora gossypiella Saunders (pink bollworm), Phyllocnistiscitrella Stainton (citrus leafminer), Pieris brassicae Linnaeus (largewhite butterfly), Pieris rapae Linnaeus (small white butterfly),Plutella xylostella Linnaeus (diamondback moth), Spodoptera exiguaHübner (beet armyworm), Spodoptera litura Fabricius (tobacco cutworm,cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm),Trichoplusia ni Hübner (cabbage looper) and Tuta absoluta Meyrick(tomato leafminer)).

Compounds of the invention have significant activity on members from theorder Homoptera including: Acyrthosiphon pisum Harris (pea aphid), Aphiscraccivora Koch (cowpea aphid), Aphisfabae Scopoli (black bean aphid),Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer(apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solaniKaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell(strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheataphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosomalanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy(mealy plum aphid), Lipaphis erysimi Kaltenbach (turnip aphid),Metopolophium dirrhodum Walker (cereal aphid), Macrosiphum euphorbiaeThomas (potato aphid), Myzus persicae Sulzer (peach-potato aphid, greenpeach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigusspp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (cornleaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid),Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius(English grain aphid), Therioaphis maculata Buckton (spotted alfalfaaphid), Toxoptera aurantii Boyer de Fonscolombe (black citrus aphid),and Toxoptera citricida Kirkaldy (brown citrus aphid); Adelges spp.(adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisiatabaci Gennadius (tobacco whitefly, sweetpotato whitefly), Bemisiaargentifolii Bellows & Perring (silverleaf whitefly), Dialeurodes citriAshmead (citrus whitefly) and Trialeurodes vaporariorum Westwood(greenhouse whitefly); Empoasca fabae Harris (potato leafhopper),Laodelphax striatellus Fallen (smaller brown planthopper), Macrolestesquadrilineatus Forbes (aster leafhopper), Nephotettix cinticeps Uhler(green leafhopper), Nephotettix nigropictus Stål (rice leafhopper),Nilaparvata lugens Stål (brown planthopper), Peregrinus maidis Ashmead(corn planthopper), Sogatella furcifera Horvath (white-backedplanthopper), Sogatodes orizicola Muir (rice delphacid), Typhlocybapomaria McAtee white apple leafhopper, Erythroneoura spp. (grapeleafhoppers); Magicidada septendecim Linnaeus (periodical cicada);Icerya purchasi Maskell (cottony cushion scale), Quadraspidiotusperniciosus Comstock (San Jose scale); Planococcus citri Risso (citrusmealybug); Pseudococcus spp. (other mealybug complex); Cacopsyllapyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmonpsylla).

Compounds of this invention also have activity on members from the orderHemiptera including: Acrosternum hilare Say (green stink bug), Anasatristis De Geer (squash bug), Blissus leucopterus leucopterus Say(chinch bug), Cimex lectularius Linnaeus (bed bug) Corythuca gossypiiFabricius (cotton lace bug), Cyrtopeltis modesta Distant (tomato bug),Dysdercus suturellus Herrich-Schaffer (cotton stainer), Euchistus servusSay (brown stink bug), Euchistus variolarius Palisot de Beauvois(one-spotted stink bug), Graptosthetus spp. (complex of seed bugs),Halymorpha halys Stål (brown marmorated stink bug), Leptoglossuscorculus Say (leaf-footed pine seed bug), Lygus lineolaris Palisot deBeauvois (tarnished plant bug), Nezara viridula Linnaeus (southern greenstink bug), Oebalus pugnax Fabricius (rice stink bug), Oncopeltusfasciatus Dallas (large milkweed bug), Pseudatomoscelis seriatus Reuter(cotton fleahopper). Other insect orders controlled by compounds of theinvention include Thysanoptera (e.g., Frankliniella occidentalisPergande (western flower thrips), Scirthothrips citri Moulton (citrusthrips), Sericothrips variabilis Beach (soybean thrips), and Thripstabaci Lindeman (onion thrips); and the order Coleoptera (e.g.,Leptinotarsa decemlineata Say (Colorado potato beetle), Epilachnavarivestis Mulsant (Mexican bean beetle) and wireworms of the generaAgriotes, Athous or Limonius).

Note that some contemporary classification systems place Homoptera as asuborder within the order Hemiptera.

Of note is use of compounds of this invention for controlling westernflower thrips (Frankliniella occidentalis). Of note is use of compoundsof this invention for controlling potato leafhopper (Empoasca fabae). Ofnote is use of compounds of this invention for controlling cotton melonaphid (Aphis gossypii). Of note is use of compounds of this inventionfor controlling green peach aphid (Myzus persicae). Of note is use ofcompounds of this invention for controlling sweetpotato whitefly(Bemisia tabaci).

Compounds of the present invention may also be useful for increasingvigor of a crop plant. This method comprises contacting the crop plant(e.g., foliage, flowers, fruit or roots) or the seed from which the cropplant is grown with a compound of Formula 1 in amount sufficient toachieve the desired plant vigor effect (i.e. biologically effectiveamount). Typically the compound of Formula 1 is applied in a formulatedcomposition. Although the compound of Formula 1 is often applieddirectly to the crop plant or its seed, it can also be applied to thelocus of the crop plant, i.e. the environment of the crop plant,particularly the portion of the environment in close enough proximity toallow the compound of Formula 1 to migrate to the crop plant. The locusrelevant to this method most commonly comprises the growth medium (i.e.medium providing nutrients to the plant), typically soil in which theplant is grown. Treatment of a crop plant to increase vigor of the cropplant thus comprises contacting the crop plant, the seed from which thecrop plant is grown or the locus of the crop plant with a biologicallyeffective amount of a compound of Formula 1.

Increased crop vigor can result in one or more of the following observedeffects: (a) optimal crop establishment as demonstrated by excellentseed germination, crop emergence and crop stand; (b) enhanced cropgrowth as demonstrated by rapid and robust leaf growth (e.g., measuredby leaf area index), plant height, number of tillers (e.g., for rice),root mass and overall dry weight of vegetative mass of the crop; (c)improved crop yields, as demonstrated by time to flowering, duration offlowering, number of flowers, total biomass accumulation (i.e. yieldquantity) and/or fruit or grain grade marketability of produce (i.e.yield quality); (d) enhanced ability of the crop to withstand or preventplant disease infections and arthropod, nematode or mollusk pestinfestations; and (e) increased ability of the crop to withstandenvironmental stresses such as exposure to thermal extremes, suboptimalmoisture or phytotoxic chemicals.

The compounds of the present invention may increase the vigor of treatedplants compared to untreated plants by killing or otherwise preventingfeeding of phytophagous invertebrate pests in the environment of theplants. In the absence of such control of phytophagous invertebratepests, the pests reduce plant vigor by consuming plant tissues or sap,or transmitting plant pathogens such as viruses. Even in the absence ofphytophagous invertebrate pests, the compounds of the invention mayincrease plant vigor by modifying metabolism of plants. Generally, thevigor of a crop plant will be most significantly increased by treatingthe plant with a compound of the invention if the plant is grown in anonideal environment, i.e. an environment comprising one or more aspectsadverse to the plant achieving the full genetic potential it wouldexhibit in an ideal environment.

Of note is a method for increasing vigor of a crop plant wherein thecrop plant is grown in an environment comprising phytophagousinvertebrate pests. Also of note is a method for increasing vigor of acrop plant wherein the crop plant is grown in an environment notcomprising phytophagous invertebrate pests. Also of note is a method forincreasing vigor of a crop plant wherein the crop plant is grown in anenvironment comprising an amount of moisture less than ideal forsupporting growth of the crop plant. Of note is a method for increasingvigor of a crop plant wherein the crop is rice. Also of note is a methodfor increasing vigor of a crop plant wherein the crop is maize (corn).Also of note is a method for increasing vigor of a crop plant whereinthe crop is soybean.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including insecticides,fungicides, nematocides, bactericides, acaricides, herbicides, herbicidesafeners, growth regulators such as insect molting inhibitors androoting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, other biologically activecompounds or entomopathogenic bacteria, virus or fungi to form amulti-component pesticide giving an even broader spectrum of agronomicand nonagronomic utility. Thus the present invention also pertains to acomposition comprising a biologically effective amount of a compound ofFormula 1, at least one additional component selected from the groupconsisting of surfactants, solid diluents and liquid diluents, and atleast one additional biologically active compound or agent. For mixturesof the present invention, the other biologically active compounds oragents can be formulated together with the present compounds, includingthe compounds of Formula 1, to form a premix, or the other biologicallyactive compounds or agents can be formulated separately from the presentcompounds, including the compounds of Formula 1, and the twoformulations combined together before application (e.g., in a spraytank) or, alternatively, applied in succession.

Examples of such biologically active compounds or agents with whichcompounds of this invention can be formulated are insecticides such asabamectin, acephate, acequinocyl, acetamiprid, acrinathrin, afidopyropen([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin,bifenazate, bistrifluron, borate, buprofezin, cadusafos, carbaryl,carbofuran, cartap, carzol, chlorantraniliprole, chlorfenapyr,chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,clofentezin, clothianidin, cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyclaniliprole (3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide),cycloprothrin, cycloxaprid((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-Epoxy-1H-imidazo[1,2-a]azepine)cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dicloromezotiaz, dieldrin, diflubenzuron, dimefluthrin, dimehypo,dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide,fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate,fipronil, flometoquin(2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), flonicamid, flubendiamide, flucythrinate, flufenerim,flufenoxuron, flufenoxystrobin (methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),flufensulfone(5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole),fluhexafon, fluopyram, flupiprole(1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile),flupyradifurone(4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone),fluvalinate, tau-fluvalinate, fonophos, formetanate, fosthiazate,halofenozide, heptafluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate),hexaflumuron, hexythiazox, hydramethylnon, imidacloprid, indoxacarb,insecticidal soaps, isofenphos, lufenuron, malathion, meperfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate),metaflumizone, metaldehyde, methamidophos, methidathion, methiodicarb,methomyl, methoprene, methoxychlor, metofluthrin, methoxyfenozide,metofluthrin, monocrotophos, monofluorothrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate),nicotine, nitenpyram, nithiazine, novaluron, noviflumuron, oxamyl,parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet,phosphamidon, pirimicarb, profenofos, profluthrin, propargite,protrifenbute, pyflubumide(1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide),pymetrozine, pyrafluprole, pyrethrin, pyridaben, pyridalyl,pyrifluquinazon, pyriminostrobin (methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate),pyriprole, pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulprofos,sulfoxaflor(N-[methyloxido[1-[6-(trifluoromethyl)-3-pyridinyl]ethyl]-λ⁴-sulfanylidene]cyanamide),tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethrin, tetramethylfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2,3,3-tetramethylcyclopropanecarboxylate), tetraniliprole,thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium, tioxazafen(3-phenyl-5-(2-thienyl)-1,2,4-oxadiazole), tolfenpyrad, tralomethrin,triazamate, trichlorfon, triflumezopyrim(2,4-dioxo-1-(5-pyrimidinylmethyl)-3-[3-(trifluoromethyl)phenyl]-2H-pyrido[1,2-a]pyrimidiniuminner salt), triflumuron, Bacillus thuringiensis delta-endotoxins,entomopathogenic bacteria, entomopathogenic viruses and entomopathogenicfungi.

Of note are insecticides such as abamectin, acetamiprid, acrinathrin,afidopyropen, amitraz, avermectin, azadirachtin, benfuracarb, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyclaniliprole, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin,cypermethrin, alpha-cypermethrin, zeta-cypermethrin, cyromazine,deltamethrin, dicloromezotiaz, dieldrin, dinotefuran, diofenolan,emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox, etoxazole,fenitrothion, fenothiocarb, fenoxycarb, fenvalerate, fipronil,flometoquin, flonicamid, flubendiamide, flufenoxuron, flufenoxystrobin,flufensulfone, flupiprole, flupyradifurone, fluvalinate, formetanate,fosthiazate, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid,indoxacarb, lufenuron, meperfluthrin, metaflumizone, methiodicarb,methomyl, methoprene, methoxyfenozide, metofluthrin, monofluorothrin,nitenpyram, nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine,pyrethrin, pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen,ryanodine, spinetoram, spinosad, spirodiclofen, spiromesifen,spirotetramat, sulfoxaflor, tebufenozide, tetramethrin,tetramethylfluthrin, thiacloprid, thiamethoxam, thiodicarb,thiosultap-sodium, tralomethrin, triazamate, triflumezopyrim,triflumuron, Bacillus thuringiensis delta-endotoxins, all strains ofBacillus thuringiensis and all strains of nucleo polyhedrosis viruses.

One embodiment of biological agents for mixing with compounds of thisinvention include entomopathogenic bacteria such as Bacillusthuringiensis, and the encapsulated delta-endotoxins of Bacillusthuringiensis such as MVP® and MVPII® bioinsecticides prepared by theCellCap® process (CellCap®, MVP® and MVPII® are trademarks of MycogenCorporation, Indianapolis, Ind., USA); entomopathogenic fungi such asgreen muscardine fungus; and entomopathogenic (both naturally occurringand genetically modified) viruses including baculovirus, nucleopolyhedrovirus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV),Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus(GV) such as Cydiapomonella granulosis virus (CpGV).

Of particular note is such a combination where the other invertebratepest control active ingredient belongs to a different chemical class orhas a different site of action than the compound of Formula 1. Incertain instances, a combination with at least one other invertebratepest control active ingredient having a similar spectrum of control buta different site of action will be particularly advantageous forresistance management. Thus, a composition of the present invention canfurther comprise a biologically effective amount of at least oneadditional invertebrate pest control active ingredient having a similarspectrum of control but belonging to a different chemical class orhaving a different site of action. These additional biologically activecompounds or agents include, but are not limited to,acetylcholinesterase (AChE) inhibitors such as the carbamates methomyl,oxamyl, thiodicarb, triazamate, and the organophosphates chlorpyrifos;GABA-gated chloride channel antagonists such as the cyclodienes dieldrinand endosulfan, and the phenylpyrazoles ethiprole and fipronil; sodiumchannel modulators such as the pyrethroids bifenthrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, cypermethrin,deltamethrin, dimefluthrin, esfenvalerate, metofluthrin and profluthrin;nicotinic acetylcholinereceptor (nAChR) agonists such as theneonicotinoids acetamiprid, clothianidin, dinotefuran, imidacloprid,nitenpyram, nithiazine, thiacloprid, and thiamethoxam, and sulfoxaflor;nicotinic acetylcholine receptor (nAChR) allosteric activators such asthe spinosyns spinetoram and spinosad; chloride channel activators suchas the avermectins abamectin and emamectin; juvenile hormone mimics suchas diofenolan, methoprene, fenoxycarb and pyriproxyfen; selectivehomopteran feeding blockers such as pymetrozine and flonicamid; mitegrowth inhibitors such as etoxazole; inhibitors of mitochondrial ATPsynthase such as propargite; ucouplers of oxidative phosphorylation viadisruption of the proton gradient such as chlorfenapyr; nicotinicacetylcholine receptor (nAChR) channel blockers such as the nereistoxinanalogs cartap; inhibitors of chitin biosynthesis such as thebenzoylureas flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron and triflumuron, and buprofezin; dipteran moultingdisrupters such as cyromazine; ecdysone receptor agonists such as thediacylhydrazines methoxyfenozide and tebufenozide; octopamine receptoragonists such as amitraz; mitochondrial complex III electron transportinhibitors such as hydramethylnon; mitochondrial complex I electrontransport inhibitors such as pyridaben; voltage-dependent sodium channelblockers such as indoxacarb; inhibitors of acetyl CoA carboxylase suchas the tetronic and tetramic acids spirodiclofen, spiromesifen andspirotetramat; mitochondrial complex II electron transport inhibitorssuch as the β-ketonitriles cyenopyrafen and cyflumetofen; ryanidinereceptor modulators such as the anthranilic diamideschlorantraniliprole, cyantraniliprole and cyantraniliprole, diamidessuch as flubendiamide, and ryanodine receptor ligands such as ryanodine;compounds wherein the target site responsible for biological activity isunknown or uncharacterized such as azadirachtin, bifenazate, pyridalyl,pyrifluquinazon and triflumezopyrim; microbial disrupters of insectmidgut membranes such as Bacillus thuringensis and the delta-endotoxinsthey produce and Bacillus sphaericus; and biological agents includingnucleo polyhedro viruses (NPV) and other naturally occurring orgenetically modified insecticidal viruses.

Further examples of biologically active compounds or agents with whichcompounds of this invention can be formulated are: fungicides such asacibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine,azaconazole, azoxystrobin, benalaxyl (including benalaxyl-M), benodanil,benomyl, benthiavalicarb (including benthiavalicarb-isopropyl),benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen,blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate,carboxin, carpropamid, captafol, captan, carbendazim, chloroneb,chlorothalonil, chlozolinate, copper hydroxide, copper oxychloride,copper sulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol,dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M),dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole,etaconazole, edifenphos, enoxastrobin (also known as enestroburin),epoxiconazole, ethaboxam, ethirimol, etridiazole, famoxadone,fenamidone, fenaminstrobin, fenarimol, fenbuconazole, fenfuram,fenhexamide, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph,fenpyrazamine, fentin acetate, fentin hydroxide, ferbam, ferimzone,flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, fluoxastrobin, fluquinconazole, flusilazole,flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet,fthalide (also known as phthalide), fuberidazole, furalaxyl, furametpyr,hexaconazole, hymexazole, guazatine, imazalil, imibenconazole,iminoctadine albesilate, iminoctadine triacetate, iodicarb, ipconazole,isofetamid, iprobenfos, iprodione, iprovalicarb, isoprothiolane,isopyrazam, isotianil, kasugamycin, kresoxim-methyl, mancozeb,mandipropamid, mandestrobin, maneb, mapanipyrin, mepronil,meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole,methasulfocarb, metiram, metominostrobin, metrafenone, myclobutanil,naftitine, neo-asozin (ferric methanearsonate), nuarimol, octhilinone,ofurace, orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid,oxpoconazole, oxycarboxin, oxytetracycline, penconazole, pencycuron,penflufen, penthiopyrad, perfurazoate, phosphorous acid (including saltsthereof, e.g., fosetyl-aluminm), picoxystrobin, piperalin, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, proquinazid, prothiocarb, prothioconazole, pyraclostrobin,pyrametostrobin, pyraoxystrobin, pyrazophos, pyribencarb, pyributacarb,pyrifenox, pyriofenone, perisoxazole, pyrimethanil, pyrifenox,pyrrolnitrin, pyroquilon, quinconazole, quinmethionate, quinoxyfen,quintozene, silthiofam, sedaxane, simeconazole, spiroxamine,streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam,tecloftalam, tecnazene, terbinafine, tetraconazole, thiabendazole,thifluzamide, thiophanate, thiophanate-methyl, thiram, tiadinil,tolclofos-methyl, tolprocarb, tolyfluanid, triadimefon, triadimenol,triarimol, triazoxide, tribasic copper sulfate, triclopyricarb,tridemorph, trifloxystrobin, triflumizole, trimoprhamide tricyclazole,trifloxystrobin, triforine, triticonazole, uniconazole, validamycin,valifenalate (also known as valifenal), vinclozolin, zineb, ziram,zoxamide and1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone;nematocides such as fluazaindolizine, fluopyram, spirotetramat,thiodicarb, fosthiazate, abamectin, iprodione, fluensulfone, dimethyldisulfide, tioxazafen, 1,3-dichloropropene (1,3-D), metam (sodium andpotassium), dazomet, chloropicrin, fenamiphos, ethoprophos, cadusaphos,terbufos, imicyafos, oxamyl, carbofuran, tioxazafen, Bacillus firmus andPasteuria nishizawae; bactericides such as streptomycin; acaricides suchas amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol,dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin,fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad.

In certain instances, combinations of a compound of this invention withother biologically active (particularly invertebrate pest control)compounds or agents (i.e. active ingredients) can result in agreater-than-additive (i.e. synergistic) effect. Reducing the quantityof active ingredients released in the environment while ensuringeffective pest control is always desirable. When synergism ofinvertebrate pest control active ingredients occurs at application ratesgiving agronomically satisfactory levels of invertebrate pest control,such combinations can be advantageous for reducing crop production costand decreasing environmental load.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). Such anapplication may provide a broader spectrum of plant protection and beadvantageous for resistance management. The effect of the exogenouslyapplied invertebrate pest control compounds of this invention may besynergistic with the expressed toxin proteins.

General references for these agricultural protectants (i.e.insecticides, fungicides, nematocides, acaricides, herbicides andbiological agents) include The Pesticide Manual, 13th Edition, C. D. S.Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K.,2003 and The BioPesticide Manual, 2^(nd) Edition, L. G. Copping, Ed.,British Crop Protection Council, Farnham, Surrey, U.K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity. It will be evident thatincluding these additional components can expand the spectrum ofinvertebrate pests controlled beyond the spectrum controlled by thecompound of Formula 1 alone.

Table A lists specific combinations of a compound of Formula 1 withother invertebrate pest control agents illustrative of the mixtures,compositions and methods of the present invention. The first column ofTable A lists the specific invertebrate pest control agents (e.g.,“Abamectin” in the first line). The second column of Table A lists themode of action (if known) or chemical class of the invertebrate pestcontrol agents. The third column of Table A lists embodiment(s) ofranges of weight ratios for rates at which the invertebrate pest controlagent can be applied relative to a compound of Formula 1 (e.g., “50:1 to1:50” of abamectin relative to a compound of Formula 1 by weight). Thus,for example, the first line of Table A specifically discloses thecombination of a compound of Formula 1 with abamectin can be applied ina weight ratio between 50:1 to 1:50. The remaining lines of Table A areto be construed similarly. Of further note Table A lists specificcombinations of a compound of Formula 1 with other invertebrate pestcontrol agents illustrative of the mixtures, compositions and methods ofthe present invention and includes additional embodiments of weightratio ranges for application rates.

TABLE A Invertebrate Pest Mode of Action or Typical Control AgentChemical Class Weight Ratio Abamectin chloride channel activator 50:1 to1:50 Acetamiprid nicotinic acetylcholinereceptor 150:1 to 1:200 (nAChR)agonist Amitraz octopamine receptor agonists 200:1 to 1:100 Avermectinmacrocyclic lactones 50:1 to 1:50 Azadirachtin unknown site of action100:1 to 1:120 Beta-cyfluthrin sodium channel modulators 150:1 to 1:200Bifenthrin sodium channel modulators 100:1 to 1:10 Buprofezin chitinbiosynthesis inhibitors 500:1 to 1:50 Cartap nicotinic acetylcholinereceptor 100:1 to 1:200 (nAChR) channel blocker Chlorantraniliproleryanodine receptor modulator 100:1 to 1:120 Chlorfenapyr uncouplers ofoxidative 300:1 to 1:200 phosphorylation Chlorpyrifosacetylcholinesterase inhibitor 500:1 to 1:200 Clothianidin nicotinicacetylcholine receptor 100:1 to 1:400 (nAChR) agonist CyantraniliproleRyanodine receptor modulator 100:1 to 1:120 Cyfluthrin sodium channelmodulator 150:1 to 1:200 Cyhalothrin sodium channel modulator 150:1 to1:200 Cypermethrin sodium channel modulator 150:1 to 1:200 Cyromazinedipteran moulting disrupter 400:1 to 1:50 Deltamethrin sodium channelmodulators 50:1 to 1:400 Dicloromezotiaz Dieldrin GABA-gated chloride200:1 to 1:100 channel antagonist Dinotefuran nicotinic acetylcholinereceptor 150:1 to 1:200 (nAChR) agonist Diofenolan juvenile hormonemimic 150:1 to 1:200 Emamectin chloride channel activator 50:1 to 1:10Endosulfan GABA-gated chloride 200:1 to 1:100 channel antagonistEsfenvalerate sodium channel modulator 100:1 to 1:400 EthiproleGABA-regulated chloride 200:1 to 1:100 channel antagonist Fenothiocarb150:1 to 1:200 Fenoxycarb juvenile hormone mimic 500:1 to 1:100Fenvalerate sodium channel modulator 150:1 to 1:200 FipronilGABA-regulated chloride 150:1 to 1:100 channel antagonist Flonicamidselective homopteran feeding 200:1 to 1:100 blocker Flubendiamideryanodine receptor modulator 100:1 to 1:120 Flufenoxuron chitinbiosynthesis inhibitor 200:1 to 1:100 Hexaflumuron chitin biosynthesisinhibitor 300:1 to 1:50 Hydramethylnon mitochondrial Complex III 150:1to 1:250 electron transport inhibitors Imidacloprid nicotinicacetylcholine receptor 1000:1 to 1:1000 (nAChR) agonist Indoxacarbvoltage-dependent sodium 200:1 to 1:50 channel blockerLambda-cyhalothrin sodium channel modulator 50:1 to 1:250 Lufenuronchitin biosynthesis inhibitor 500:1 to 1:250 Metaflumizonevoltage-dependent sodium 200:1 to 1:200 channel blocker Methomylacetylcholinesterase inhibitor 500:1 to 1:100 Methoprene juvenilehormone mimic 500:1 to 1:100 Methoxyfenozide ecdysone receptor agonist50:1 to 1:50 Nitenpyram nicotinic acetylcholine receptor 150:1 to 1:200(nAChR) agonist Nithiazine nicotinic acetylcholine receptor 150:1 to1:200 (nAChR) agonist Novaluron chitin biosynthesis inhibitor 500:1 to1:150 Oxamyl acetylcholinesterase inhibitors 200:1 to 1:200 Pymetrozineselective homopteran feeding 200:1 to 1:100 blocker Pyrethrin sodiumchannel modulator 100:1 to 1:10 Pyridaben mitochondrial Complex I 200:1to 1:100 electron transport inhibitor Pyridalyl unknown site of action200:1 to 1:100 Pyriproxyfen juvenile hormone mimic 500:1 to 1:100Ryanodine ryanodine receptor ligand 100:1 to 1:120 Spinetoram nicotinicacetylcholine receptor 150:1 to 1:100 (nAChR) allosteric activatorSpinosad nicotinic acetylcholine receptor 500:1 to 1:10 (nAChR)allosteric activators Spirodiclofen acetyl CoA carboxylase inhibitor200:1 to 1:200 Spiromesifen acetyl CoA carboxylase inhibitor 200:1 to1:200 Tebufenozide ecdysone receptor agonist 500:1 to 1:250 Thiaclopridnicotinic acetylcholine receptor 100:1 to 1:200 (nAChR) agonistThiamethoxam nicotinic acetylcholine receptor 1250:1 to 1:1000 (nAChR)agonist Thiodicarb acetylcholinesterase inhibitors 500:1 to 1:400Thiosultap-sodium Nicotinic acetylcholine receptor 150:1 to 1:100(nAChR) channel blocker Tralomethrin sodium channel modulator 150:1 to1:200 Triazamate acetyl cholinesterase inhibitors 250:1 to 1:100Triflumezopyrim Triflumuron chitin synthesis inhibitor 200:1 to 1:100Bacillus biological agents 50:1 to 1:10 thuringiensis Bacillusbiological agents 50:1 to 1:10 thuringiensis delta-endotoxin NPV (e.g.,Gemstar) biological agents 50:1 to 1:10

Of note is the composition of the present invention wherein the at leastone additional biologically active compound or agent is selected fromthe Invertebrate Pest Control Agents listed in Table A above.

The weight ratios of a compound, including a compound of Formula 1, anN-oxide or a salt thereof, to the additional invertebrate pest controlagent typically are between 1000:1 and 1:1000, with one embodiment beingbetween 500:1 and 1:500, another embodiment being between 250:1 and1:200 and another embodiment being between 100:1 and 1:50.

Listed below in Tables B1 to B14 are embodiments of specificcompositions comprising a compound of Formula 1 (compound numbers referto compounds in Index Tables A and B) and an additional invertebratepest control agent.

TABLE B1 Mixture Cmpd. Invertebrate Pest No. No. and Control Agent B1-17 and Abamectin B1-2 7 and Acetamiprid B1-3 7 and Amitraz B1-4 7 andAvermectin B1-5 7 and Azadirachtin B1-6 7 and Bensultap B1-7 7 andBeta-cyfluthrin B1-8 7 and Bifenthrin B1-9 7 and Buprofezin B1-10 7 andCartap B1-11 7 and Chlorantraniliprole B1-12 7 and Chlorfenapyr B1-13 7and Chlorpyrifos B1-14 7 and Clothianidin B1-15 7 and CyantraniliproleB1-16 7 and Cyfluthrin B1-17 7 and Cyhalothrin B1-18 7 and CypermethrinB1-19 7 and Cyromazine B1-20 7 and Deltamethrin B1-21 7 andDicloromezotiaz B1-21a 7 and Dieldrin B1-22 7 and Dinotefuran B1-23 7and Diofenolan B1-24 7 and Emamectin B1-25 7 and Endosulfan B1-26 7 andEsfenvalerate B1-27 7 and Ethiprole B1-28 7 and Fenothiocarb B1-29 7 andFenoxycarb B1-30 7 and Fenvalerate B1-31 7 and Fipronil B1-32 7 andFlonicamid B1-33 7 and Flubendiamide B1-34 7 and Flufenoxuron B1-35 7and Hexaflumuron B1-36 7 and Hydramethylnon B1-37 7 and ImidaclopridB1-38 7 and Indoxacarb B1-39 7 and Lambda-cyhalothrin B1-40 7 andLufenuron B1-41 7 and Metaflumizone B1-42 7 and Methomyl B1-43 7 andMethoprene B1-44 7 and Methoxyfenozide B1-45 7 and Nitenpyram B1-46 7and Nithiazine B1-47 7 and Novaluron B1-48 7 and Oxamyl B1-49 7 andPhosmet B1-50 7 and Pymetrozine B1-51 7 and Pyrethrin B1-52 7 andPyridaben B1-53 7 and Pyridalyl B1-54 7 and Pyriproxyfen B1-55 7 andRyanodine B1-56 7 and Spinetoram B1-57 7 and Spinosad B1-58 7 andSpirodiclofen B1-59 7 and Spiromesifen B1-60 7 and Spirotetramat B1-61 7and Sulfoxaflor B1-62 7 and Tebufenozide B1-63 7 and Tefluthrin B1-64 7and Thiacloprid B1-65 7 and Thiamethoxam B1-66 7 and Thiodicarb B1-67 7and Thiosultap-sodium B1-68 7 and Tolfenpyrad B1-69 7 and TralomethrinB1-70 7 and Triazamate B1-71 7 and Triflumezopyrim B1-72 7 andTriflumuron B1-73 7 and Bacillus thuringiensis B1-74 7 and Bacillusthuringiensis delta-endotoxin B1-75 7 and NPV (e.g., Gemstar)

Table B2

Table B2 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 8. For example, the first mixture in Table B2 is designatedB2-1 and is a mixture of compound 8 and the additional invertebrate pestcontrol agent abamectin.

Table B3

Table B3 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 9. For example, the first mixture in Table B3 is designatedB3-1 and is a mixture of compound 9 and the additional invertebrate pestcontrol agent abamectin.

Table B4

Table B4 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 10. For example, the first mixture in Table B4 is designatedB4-1 and is a mixture of compound 10 and the additional invertebratepest control agent abamectin.

Table B5

Table B5 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 14. For example, the first mixture in Table B5 is designatedB5-1 and is a mixture of compound 14 and the additional invertebratepest control agent abamectin.

Table B6

Table B6 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 15. For example, the first mixture in Table B6 is designatedB6-1 and is a mixture of compound 15 and the additional invertebratepest control agent abamectin.

Table B7

Table B7 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 16. For example, the first mixture in Table B7 is designatedB7-1 and is a mixture of compound 16 and the additional invertebratepest control agent abamectin.

Table B8

Table B8 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 18. For example, the first mixture in Table B8 is designatedB8-1 and is a mixture of compound 18 and the additional invertebratepest control agent abamectin.

Table B9

Table B9 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 20. For example, the first mixture in Table B9 is designatedB9-1 and is a mixture of compound 20 and the additional invertebratepest control agent abamectin.

Table B10

Table B10 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 30. For example, the first mixture in Table B10 isdesignated B10-1 and is a mixture of compound 30 and the additionalinvertebrate pest control agent abamectin.

Table B11

Table B11 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 32. For example, the first mixture in Table B11 isdesignated B11-1 and is a mixture of compound 32 and the additionalinvertebrate pest control agent abamectin.

Table B12

Table B12 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 35. For example, the first mixture in Table B12 isdesignated B12-1 and is a mixture of compound 35 and the additionalinvertebrate pest control agent abamectin.

Table B13

Table B13 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 38. For example, the first mixture in Table B13 isdesignated B13-1 and is a mixture of compound 38 and the additionalinvertebrate pest control agent abamectin.

Table B14

Table B14 is identical to Table B1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 39. For example, the first mixture in Table B14 isdesignated B14-1 and is a mixture of compound 39 and the additionalinvertebrate pest control agent abamectin.

The specific mixtures listed in Tables B1 to B14 typically combine acompound of Formula 1 with the other invertebrate pest agent in theratios specified in Table A.

Listed below in Tables C1 to C14 are specific mixtures comprising acompound of Formula 1 (compound numbers (Cmpd. No.) refer to compoundsin Index Tables A and B) and an additional invertebrate pest controlagent. Tables C1 to C14 further list specific weight ratios typical ofthe mixtures of Tables C1 to C14. For example, the first weight ratioentry of the first line of Table C1 specifically discloses the mixtureof Compound 7 of Index Table A with abamectin applied in a weight ratioof 100 parts Compound 7 to 1 part abamectin.

TABLE C1 Mixture Cmpd. Invertebrate Pest No. No. and Control AgentTypical Mixture Ratios (by weight) C1-1 7 and Abamectin 100:1 10:1 5:12:1 1:1 1:2 1:5 1:10 1:100 C1-2 7 and Acetamiprid 100:1 10:1 5:1 2:1 1:11:2 1:5 1:10 1:100 C1-3 7 and Amitraz 100:1 10:1 5:1 2:1 1:1 1:2 1:51:10 1:100 C1-4 7 and Avermectin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:101:100 C1-5 7 and Azadirachtin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100C1-6 7 and Bensultap 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-7 7and Beta-cyfluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-8 7 andBifenthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-9 7 andBuprofezin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-10 7 and Cartap100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-11 7 andChlorantraniliprole 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-12 7and Chlorfenapyr 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-13 7 andChlorpyrifos 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-14 7 andClothianidin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-15 7 andCyantraniliprole 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-16 7 andCyfluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-17 7 andCyhalothrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-18 7 andCypermethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-19 7 andCyromazine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-20 7 andDeltamethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-20a 7 andDicloromezotiaz 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-21 7 andDieldrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-22 7 andDinotefuran 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-23 7 andDiofenolan 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-24 7 andEmamectin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-25 7 andEndosulfan 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-26 7 andEsfenvalerate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-27 7 andEthiprole 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-28 7 andFenothiocarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-29 7 andFenoxycarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-30 7 andFenvalerate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-31 7 andFipronil 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-32 7 andFlonicamid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-33 7 andFlubendiamide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-34 7 andFlufenoxuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-35 7 andHexaflumuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-36 7 andHydramethylnon 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-37 7 andImidacloprid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-38 7 andIndoxacarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-39 7 and Lambda-100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 cyhalothrin C1-40 7 andLufenuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-41 7 andMetaflumizone 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-42 7 andMethomyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-43 7 andMethoprene 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-44 7 andMethoxyfenozide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-45 7 andNitenpyram 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-46 7 andNithiazine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-47 7 andNovaluron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-48 7 and Oxamyl100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-49 7 and Phosmet 100:1 10:15:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-50 7 and Pymetrozine 100:1 10:1 5:12:1 1:1 1:2 1:5 1:10 1:100 C1-51 7 and Pyrethrin 100:1 10:1 5:1 2:1 1:11:2 1:5 1:10 1:100 C1-52 7 and Pyridaben 100:1 10:1 5:1 2:1 1:1 1:2 1:51:10 1:100 C1-53 7 and Pyridalyl 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:101:100 C1-54 7 and Pyriproxyfen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100C1-55 7 and Ryanodine 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-56 7and Spinetoram 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-57 7 andSpinosad 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-58 7 andSpirodiclofen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-59 7 andSpiromesifen 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-60 7 andSpirotetramat 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-61 7 andSulfoxaflor 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-62 7 andTebufenozide 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-63 7 andTefluthrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-64 7 andThiacloprid 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-65 7 andThiamethoxam 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-66 7 andThiodicarb 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-67 7 andThiosultap-sodium 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-68 7 andTolfenpyrad 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-69 7 andTralomethrin 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-70 7 andTriazamate 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-71 7 andTriflumezopyrim 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-72 7 andTriflumuron 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 C1-73 7 andBacillus 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 thuringiensis C1-74 7and Bacillus 100:1 10:1 5:1 2:1 1:1 1:2 1:5 1:10 1:100 thuringiensisdelta-endotoxin C1-75 7 and NPV (e.g., 100:1 10:1 5:1 2:1 1:1 1:2 1:51:10 1:100 Gemstar)

Table C2

Table C2 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 8. For example, the first weight ratio entry of the firstline of Table C2 specifically discloses the mixture of Compound 8 withabamectin applied in a weight ratio of 100 parts Compound 8 to 1 partabamectin.

Table C3

Table C3 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 9. For example, the first weight ratio entry of the firstline of Table C3 specifically discloses the mixture of Compound 9 withabamectin applied in a weight ratio of 100 parts Compound 9 to 1 partabamectin.

Table C4

Table C4 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 10. For example, the first weight ratio entry of the firstline of Table C4 specifically discloses the mixture of Compound 10 withabamectin applied in a weight ratio of 100 parts Compound 10 to 1 partabamectin.

Table C5

Table C5 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 14. For example, the first weight ratio entry of the firstline of Table C5 specifically discloses the mixture of Compound 14 withabamectin applied in a weight ratio of 100 parts Compound 14 to 1 partabamectin.

Table C6

Table C6 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 15. For example, the first weight ratio entry of the firstline of Table C6 specifically discloses the mixture of Compound 15 withabamectin applied in a weight ratio of 100 parts Compound 15 to 1 partabamectin.

Table C7

Table C7 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 16. For example, the first weight ratio entry of the firstline of Table C7 specifically discloses the mixture of Compound 16 withabamectin applied in a weight ratio of 100 parts Compound 16 to 1 partabamectin.

Table C8

Table C8 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 18. For example, the first weight ratio entry of the firstline of Table C8 specifically discloses the mixture of Compound 18 withabamectin applied in a weight ratio of 100 parts Compound 18 to 1 partabamectin.

Table C9

Table C9 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 20. For example, the first weight ratio entry of the firstline of Table C9 specifically discloses the mixture of Compound 20 withabamectin applied in a weight ratio of 100 parts Compound 20 to 1 partabamectin.

Table C10

Table C10 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 30. For example, the first weight ratio entry of the firstline of Table C10 specifically discloses the mixture of Compound 30 withabamectin applied in a weight ratio of 100 parts Compound 30 to 1 partabamectin.

Table C11

Table C11 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 32. For example, the first weight ratio entry of the firstline of Table C11 specifically discloses the mixture of Compound 32 withabamectin applied in a weight ratio of 100 parts Compound 32 to 1 partabamectin.

Table C12

Table C12 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 35. For example, the first weight ratio entry of the firstline of Table C12 specifically discloses the mixture of Compound 35 withabamectin applied in a weight ratio of 100 parts Compound 35 to 1 partabamectin.

Table C13

Table C13 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 38. For example, the first weight ratio entry of the firstline of Table C13 specifically discloses the mixture of Compound 38 withabamectin applied in a weight ratio of 100 parts Compound 38 to 1 partabamectin.

Table C14

Table C14 is identical to Table C1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 39. For example, the first weight ratio entry of the firstline of Table C14 specifically discloses the mixture of Compound 39 withabamectin applied in a weight ratio of 100 parts Compound 39 to 1 partabamectin.

Listed below in Tables D1 to D14 are embodiments of specificcompositions comprising a compound of Formula 1 (compound numbers (Cmpd.No.) refer to compounds in Index Tables A and B) and an additionalfungicide.

TABLE D1 Mixture Cmpd. No. No. and Fungicide D1-1 7 and Probenazole D1-27 and Tiadinil D1-3 7 and Isotianil D1-4 7 and Pyroquilon D1-5 7 andMetominostrobin D1-6 7 and Flutolanil D1-7 7 and Validamycin D1-8 7 andFurametpyr D1-9 7 and Pencycuron D1-10 7 and Simeconazole D1-11 7 andOrysastrobin D1-12 7 and Trifloxystrobin D1-13 7 and IsoprothiolaneD1-14 7 and Azoxystrobin D1-15 7 and Tricyclazole D1-16 7 andHexaconazole D1-17 7 and Difenoconazole D1-18 7 and Cyproconazole D1-197 and Propiconazole D1-20 7 and Fenoxanil D1-21 7 and Ferimzone D1-22 7and Fthalide D1-23 7 and Kasugamycin D1-24 7 and Picoxystrobin D1-25 7and Penthiopyrad D1-26 7 and Famoxadone D1-27 7 and Cymoxanil D1-28 7and Proquinazid D1-29 7 and Flusilazole D1-30 7 and Mancozeb D1-31 7 andCopper hydroxide D1-32 7 and Oxathiapiprolin

Table D2

Table D2 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 8. For example, the first mixture in Table D2 is designatedD2-1 and is a mixture of compound 8 and the additional fungicideprobenazole.

Table D3

Table D3 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 9. For example, the first mixture in Table D3 is designatedD3-1 and is a mixture of compound 9 and the additional fungicideprobenazole.

Table D4

Table D4 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 10. For example, the first mixture in Table D4 is designatedD4-1 and is a mixture of compound 10 and the additional fungicideprobenazole.

Table D5

Table D5 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 14. For example, the first mixture in Table D5 is designatedD5-1 and is a mixture of compound 14 and the additional fungicideprobenazole.

Table D6

Table D6 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 15. For example, the first mixture in Table D6 is designatedD6-1 and is a mixture of compound 15 and the additional fungicideprobenazole.

Table D7

Table D7 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 16. For example, the first mixture in Table D7 is designatedD7-1 and is a mixture of compound 16 and the additional fungicideprobenazole.

Table D8

Table D8 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 18. For example, the first mixture in Table D8 is designatedD8-1 and is a mixture of compound 18 and the additional fungicideprobenazole.

Table D9

Table D9 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 20. For example, the first mixture in Table D9 is designatedD9-1 and is a mixture of compound 20 and the additional fungicideprobenazole.

Table D10

Table D10 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 30. For example, the first mixture in Table D10 isdesignated D10-1 and is a mixture of compound 30 and the additionalfungicide probenazole.

Table D11

Table D11 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 32. For example, the first mixture in Table D11 isdesignated D11-1 and is a mixture of compound 32 and the additionalfungicide probenazole.

Table D12

Table D12 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 35. For example, the first mixture in Table D12 isdesignated D12-1 and is a mixture of compound 35 and the additionalfungicide probenazole.

Table D13

Table D13 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 38. For example, the first mixture in Table D13 isdesignated D13-1 and is a mixture of compound 38 and the additionalfungicide probenazole.

Table D14

Table D14 is identical to Table D1, except that each reference tocompound 7 in the column headed “Cmpd. No.” is replaced by a referenceto compound 39. For example, the first mixture in Table D14 isdesignated D14-1 and is a mixture of compound 39 and the additionalfungicide probenazole.

Invertebrate pests are controlled in agronomic and nonagronomicapplications by applying one or more compounds of this invention,typically in the form of a composition, in a biologically effectiveamount, to the environment of the pests, including the agronomic and/ornonagronomic locus of infestation, to the area to be protected, ordirectly on the pests to be controlled.

Thus the present invention comprises a method for controlling aninvertebrate pest in agronomic and/or nonagronomic applications,comprising contacting the invertebrate pest or its environment with abiologically effective amount of one or more of the compounds of theinvention, or with a composition comprising at least one such compoundor a composition comprising at least one such compound and abiologically effective amount of at least one additional biologicallyactive compound or agent. Examples of suitable compositions comprising acompound of the invention and a biologically effective amount of atleast one additional biologically active compound or agent includegranular compositions wherein the additional active compound is presenton the same granule as the compound of the invention or on granulesseparate from those of the compound of the invention.

To achieve contact with a compound or composition of the invention toprotect a field crop from invertebrate pests, the compound orcomposition is typically applied to the seed of the crop beforeplanting, to the foliage (e.g., leaves, stems, flowers, fruits) of cropplants, or to the soil or other growth medium before or after the cropis planted.

One embodiment of a method of contact is by spraying. Alternatively, agranular composition comprising a compound of the invention can beapplied to the plant foliage or the soil. Compounds of this inventioncan also be effectively delivered through plant uptake by contacting theplant with a composition comprising a compound of this invention appliedas a soil drench of a liquid formulation, a granular formulation to thesoil, a nursery box treatment or a dip of transplants. Of note is acomposition of the present invention in the form of a soil drench liquidformulation. Also of note is a method for controlling an invertebratepest comprising contacting the invertebrate pest or its environment witha biologically effective amount of a compound of the present inventionor with a composition comprising a biologically effective amount of acompound of the present invention. Of further note is this methodwherein the environment is soil and the composition is applied to thesoil as a soil drench formulation. Of further note is that compounds ofthis invention are also effective by localized application to the locusof infestation. Other methods of contact include application of acompound or a composition of the invention by direct and residualsprays, aerial sprays, gels, seed coatings, microencapsulations,systemic uptake, baits, ear tags, boluses, foggers, fumigants, aerosols,dusts and many others. One embodiment of a method of contact is adimensionally stable fertilizer granule, stick or tablet comprising acompound or composition of the invention. The compounds of thisinvention can also be impregnated into materials for fabricatinginvertebrate control devices (e.g., insect netting).

Compounds of the invention are useful in treating all plants, plantparts and seeds. Plant and seed varieties and cultivars can be obtainedby conventional propagation and breeding methods or by geneticengineering methods. Genetically modified plants or seeds (transgenicplants or seeds) are those in which a heterologous gene (transgene) hasbeen stably integrated into the plant's or seed's genome. A transgenethat is defined by its particular location in the plant genome is calleda transformation or transgenic event.

Genetically modified plant and seed cultivars which can be treatedaccording to the invention include those that are resistant against oneor more biotic stresses (pests such as nematodes, insects, mites, fungi,etc.) or abiotic stresses (drought, cold temperature, soil salinity,etc.), or that contain other desirable characteristics. Plants and seedscan be genetically modified to exhibit traits of, for example, herbicidetolerance, insect-resistance, modified oil profiles or droughttolerance. Useful genetically modified plants and seeds containingsingle gene transformation events or combinations of transformationevents are listed in Table Z. Additional information for the geneticmodifications listed in Table Z can be obtained from the followingdatabases:

http://www2.oecd.org/biotech/byidentifier.aspx

http://www.aphis.usda.go

http://gmoinfo.jrc.ec.europa.eu

The following abbreviations are used in Table Z which follows: tol. istolerance, res. is resistance, SU is sulfonylurea, ALS is acetolactatesynthase, HPPD is 4-Hydroxyphenylpyruvate Dioxygenase, NA is NotAvailable?

TABLE Z Crop Event Name Event Code Trait(s) Gene(s) Alfalfa J101MON-00101-8 Glyphosate tol. cp4 epsps (aroA:CP4) Alfalfa J163MON-ØØ163-7 Glyphosate tol. cp4 epsps (aroA:CP4) Canola* 23-18-17 (EventCGN-89465-2 High lauric acid oil te 18) Canola* 23-198 (Event 23)CGN-89465-2 High lauric acid oil te Canola* 61061 DP-Ø61Ø61-7 Glyphosatetol. gat4621 Canola* 73496 DP-Ø73496-4 Glyphosate tol. gat4621 Canola*GT200 (RT200) MON-89249-2 Glyphosate tol. cp4 epsps (aroA:CP4); goxv247Canola* GT73 (RT73) MON-ØØØ73-7 Glyphosate tol. cp4 epsps (aroA:CP4);goxv247 Canola* HCN10 (Topas NA Glufosinate tol. bar 19/2) Canola* HCN28(T45) ACS-BNØØ8-2 Glufosinate tol. pat (syn) Canola* HCN92 (TopasACS-BNØØ7-1 Glufosinate tol. bar 19/2) Canola* MON88302 MON-883Ø2-9Glyphosate tol. cp4 epsps (aroA:CP4) Canola* MPS961 NA Phytate breakdownphyA Canola* MPS962 NA Phytate breakdown phyA Canola* MPS963 NA Phytatebreakdown phyA Canola* MPS964 NA Phytate breakdown phyA Canola* MPS965NA Phytate breakdown phyA Canola* MS1 (B91-4) ACS-BNØØ4-7 Glufosinatetol. bar Canola* MS8 ACS-BNØØ5-8 Glufosinate tol. bar Canola* OXY-235ACS-BNØ11-5 Oxynil tol. bxn Canola* PHY14 NA Glufosinate tol. barCanola* PHY23 NA Glufosinate tol. bar Canola* PHY35 NA Glufosinate tol.bar Canola* PHY36 NA Glufosinate tol. bar Canola* RF1 (B93-101)ACS-BNØØ1-4 Glufosinate tol. bar Canola* RF2 (B94-2) ACS-BNØØ2-5Glufosinate tol. bar Canola* RF3 ACS-BNØØ3-6 Glufosinate tol. bar BeanEMBRAPA 5.1 EMB-PV051-1 Disease res. ac1 (sense and antisense) BrinjalEE-1 Insect res. cry1Ac (Eggplant) Carnation 11 (7442) FLO-07442-4 SUtol..; modified flower surB; dfr; hfl (f3′5′h) color Carnation 11363(1363A) FLO-11363-1 SU tol.; modified flower surB; dfr; bp40 (f3′5′h)color Carnation 1226A (11226) FLO-11226-8 SU tol.; modified flower surB;dfr; bp40 (f3′5′h) color Carnation 123.2.2 (40619) FLO-4Ø619-7 SU tol.;modified flower surB; dfr; hfl (f3′5′h) color Carnation 123.2.38 (40644)FLO-4Ø644-4 SU tol.; modified flower surB; dfr; hfl (f3′5′h) colorCarnation 123.8.12 FLO-4Ø689-6 SU tol.; modified flower surB; dfr; bp40(f3′5′h) color Carnation 123.8.8 (40685) FLO-4Ø685-1 SU tol.; modifiedflower surB; dfr; bp40 (f3′5′h) color Carnation 1351A (11351)FLO-11351-7 SU tol.; modified flower surB; dfr; bp40 (f3′5′h) colorCarnation 1400A (11400) FLO-114ØØ-2 SU tol.; modified flower surB; dfr;bp40 (f3′5′h) color Carnation 15 FLO-ØØØ15-2 SU tol.; modified flowersurB; dfr; hfl (f3′5′h) color Carnation 16 FLO-ØØØ16-3 SU tol.; modifiedflower surB; dfr; hfl (f3′5′h) color Carnation 4 FLO-ØØØØ4-9 SU tol.;modified flower surB; dfr; hfl (f3′5′h) color Carnation 66 FLO-ØØØ66-8SU tol.; delayed senescence surB; acc Carnation 959A (11959) FLO-11959-3SU tol.; modified flower surB; dfr; bp40 (f3′5′h) color Carnation 988A(11988) FLO-11988-7 SU tol.; modified flower surB; dfr; bp40 (f3′5′h)color Carnation 26407 IFD-26497-2 SU tol.; modified flower surB; dfr;bp40 (f3′5′h) color Carnation 25958 IFD-25958-3 SU tol.; modified flowersurB; dfr; bp40 (f3′5′h) color Chicory RM3-3 NA Glufosinate tol. barChicory RM3-4 NA Glufosinate tol. bar Chicory RM3-6 NA Glufosinate tol.bar Cotton 19-51a DD-Ø1951A-7 ALS herbicide tol. S4-HrA Cotton281-24-236 DAS-24236-5 Glufosinate tol.; insect res. pat (syn); cry1FCotton 3006-210-23 DAS-21Ø23-5 Glufosinate tol.; insect res. pat (syn);cry1Ac Cotton 31707 NA Oxynil tol.; insect res. bxn; cry1Ac Cotton 31803NA Oxynil tol.; insect res. bxn; cry1Ac Cotton 31807 NA Oxynil tol.;insect res. bxn; cry1Ac Cotton 31808 NA Oxynil tol.; insect res. bxn;cry1Ac Cotton 42317 NA Oxynil tol.; insect res. bxn; cry1Ac CottonBNLA-601 NA Insect res. cry1Ac Cotton BXN10211 BXN10211-9 Oxynil tol.bxn; cry1Ac Cotton BXN10215 BXN10215-4 Oxynil tol. bxn; cry1Ac CottonBXN10222 BXN10222-2 Oxynil tol. bxn; cry1Ac Cotton BXN10224 BXN10224-4Oxynil tol. bxn; cry1Ac Cotton COT102 SYN-IR102-7 Insect res. vip3A(a)Cotton COT67B SYN-IR67B-1 Insect res. cry1Ab Cotton COT202 Insect res.vip3A Cotton Event 1 NA Insect res. cry1Ac Cotton GMF Cry1A GTL-GMF311-7Insect res. cry1Ab-Ac Cotton GHB119 BCS-GH005-8 Insect res. cry2AeCotton GHB614 BCS-GH002-5 Glyphosate tol. 2mepsps Cotton GK12 NA Insectres. cry1Ab-Ac Cotton LLCotton25 ACS-GH001-3 Glufosinate tol. bar CottonMLS 9124 NA Insect res. cry1C Cotton MON1076 MON-89924-2 Insect res.cry1Ac Cotton MON1445 MON-01445-2 Glyphosate tol. cp4 epsps (aroA:CP4)Cotton MON15985 MON-15985-7 Insect res. cry1Ac; cry2Ab2 Cotton MON1698MON-89383-1 Glyphosate tol. cp4 epsps (aroA:CP4) Cotton MON531MON-00531-6 Insect res. cry1Ac Cotton MON757 MON-00757-7 Insect res.cry1Ac Cotton MON88913 MON-88913-8 Glyphosate tol. cp4 epsps (aroA:CP4)Cotton Nqwe Chi 6 Bt NA Insect res. NA? Cotton SKG321 NA Insect res.cry1A; CpTI Cotton T303-3 BCS-GH003-6 Insect res.; glufosinate tol.cry1Ab; bar Cotton T304-40 BCS-GH004-7 Insect res.; glufosinate tol.cry1Ab; bar Cotton CE43-67B Insect res. cry1Ab Cotton CE46-02A Insectres. cry1Ab Cotton CE44-69D Insect res. cry1Ab Cotton 1143-14A Insectres. cry1Ab Cotton 1143-51B Insect res. cry1Ab Cotton T342-142 Insectres. cry1Ab Cotton PV-GHGT07 Glyphosate tol. cp4 epsps (aroA:CP4) (1445)Cotton EE-GH3 Glyphosate tol. mepsps Cotton EE-GH5 Insect res. cry1AbCotton MON88701 MON-88701-3 Dicamba & glufosinate tol. Modified dmo; barCotton OsCr11 Anti-allergy Modified Cry j Creeping ASR368 SMG-368ØØ-2Glyphosate tol. cp4 epsps (aroA:CP4) Bentgrass Eucalyptus 20-C Salt tol.codA Eucalyptus 12-5C Salt tol. codA Eucalyptus 12-5B Salt tol. codAEucalyptus 107-1 Salt tol. codA Eucalyptus Jan. 9, 2001 Salt tol. codAEucalyptus Feb. 1, 2001 Salt tol. codA Eucalyptus Cold tol. des9 FlaxFP967 CDC-FL001-2 ALS herbicide tol. als Lentil RH44 Imidazolinone tol.als Maize 3272 SYN-E3272-5 Modified alpha-amylase amy797E Maize 5307SYN-05307-1 Insect res. ecry3.1Ab Maize 59122 DAS-59122-7 Insect res.;glufosinate tol. cry34Ab1; cry35Ab1; pat Maize 676 PH-000676-7Glufosinate tol.; pollination pat; dam control Maize 678 PH-000678-9Glufosinate tol.; pollination pat; dam control Maize 680 PH-000680-2Glufosinate tol.; pollination pat; dam control Maize 98140 DP-098140-6Glyphosate toll; ALS gat4621; zm-hra herbicide tol. Maize Bt10 NA Insectres.; glufosinate tol. cry1Ab; pat Maize Bt176 (176) SYN-EV176-9 Insectres.; glufosinate tol. cry1Ab; bar Maize BVLA430101 NA Phytate breakdownphyA2 Maize CBH-351 ACS-ZM004-3 Insect res.; glufosinate tol. cry9C; barMaize DAS40278-9 DAS40278-9 2,4-D tol. aad-1 Maize DBT418 DKB-89614-9Insect res.; glufosinate tol. cry1Ac; pinII; bar Maize DLL25 (B16)DKB-89790-5 Glufosinate tol. bar Maize GA21 MON-00021-9 Glyphosate tol.mepsps Maize GG25 Glyphosate tol. mepsps Maize GJ11 Glyphosate tol.mepsps Maize Fl117 Glyphosate tol. mepsps Maize GAT-ZM1 Glufosinate tol.pat Maize LY038 REN-00038-3 Increased lysine cordapA Maize MIR162SYN-IR162-4 Insect res. vip3Aa20 Maize MIR604 SYN-IR604-5 Insect res.mcry3A Maize MON801 MON801 Insect res.; glyphosate tol. cry1Ab; cp4epsps (MON80100) (aroA:CP4); goxv247 Maize MON802 MON-80200-7 Insectres.; glyphosate tol. cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON809PH-MON-809-2 Insect res.; glyphosate tol. cry1Ab; cp4 epsps (aroA:CP4);goxv247 Maize MON810 MON-00810-6 Insect res.; glyphosate tol. cry1Ab;cp4 epsps (aroA:CP4); goxv247 Maize MON832 NA Glyphosate tol. cp4 epsps(aroA:CP4); goxv247 Maize MON863 MON-00863-5 Insect res. cry3Bb1 MaizeMON87427 MON-87427-7 Glyphosate tol. cp4 epsps (aroA:CP4) Maize MON87460MON-87460-4 Drought tol. cspB Maize MON88017 MON-88017-3 Insect res.;glyphosate tol. cry3Bb1; cp4 epsps (aroA:CP4) Maize MON89034 MON-89034-3Insect res. cry2Ab2; cry1A.105 Maize MS3 ACS-ZM001-9 Glufosinate tol.;pollination bar; barnase control Maize MS6 ACS-ZM005-4 Glufosinate tol.;pollination bar; barnase control Maize NK603 MON-00603-6 Glyphosate tol.cp4 epsps (aroA:CP4) Maize T14 ACS-ZM002-1 Glufosinate tol. pat (syn)Maize T25 ACS-ZM003-2 Glufosinate tol. pat (syn) Maize TC1507DAS-01507-1 Insect res.; glufosinate tol. cry1Fa2; pat Maize TC6275DAS-06275-8 Insect res.; glufosinate tol. mocry1F; bar Maize VIP1034Insect res.; glufosinate tol. vip3A; pat Maize 43A47 DP-043A47-3 Insectres.; glufosinate tol. cry1F; cry34Ab1; cry35Ab1; pat Maize 40416DP-040416-8 Insect res.; glufosinate tol. cry1F; cry34Ab1; cry35Ab1; patMaize 32316 DP-032316-8 Insect res.; glufosinate tol. cry1F; cry34Ab1;cry35Ab1; pat Maize 4114 DP-004114-3 Insect res.; glufosinate tol.cry1F; cry34Ab1; cry35Ab1; pat Melon Melon A NA Delayedripening/senescence sam-k Melon Melon B NA Delayed ripening/senescencesam-k Papaya 55-1 CUH-CP551-8 Disease res. prsv cp Papaya 63-1CUH-CP631-7 Disease res. prsv cp Papaya Huanong No. 1 NA Disease res.prsv rep Papaya X17-2 UFL-X17CP-6 Disease res. prsv cp PetuniaPetunia-CHS NA Modified product quality CHS suppres.sion Plum C-5ARS-PLMC5-6 Disease res. ppv cp Canola** ZSR500 NA Glyphosate tol. cp4epsps (aroA:CP4); goxv247 Canola** ZSR502 NA Glyphosate tol. cp4 epsps(aroA:CP4); goxv247 Canola** ZSR503 NA Glyphosate tol. cp4 epsps(aroA:CP4); goxv247 Poplar Bt poplar NA Insect res. cry1Ac; API PoplarHybrid poplar NA Insect res. cry1Ac; API clone 741 Poplar trg300-1 Highcellulose AaXEG2 Poplar trg300-2 High cellulose AaXEG2 Potato 1210 amkNA Insect res. cry3A Potato 2904/1 kgs NA Insect res. cry3A Canola**ZSR500 NA Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Canola** ZSR502NA Glyphosate tol. cp4 epsps (aroA:CP4); goxv247 Potato ATBT04-27NMK-89367-8 Insect res. cry3A Potato ATBT04-30 NMK-89613-2 Insect res.cry3A Potato ATBT04-31 NMK-89170-9 Insect res. cry3A Potato ATBT04-36NMK-89279-1 Insect res. cry3A Potato ATBT04-6 NMK-89761-6 Insect res.cry3A Potato BT06 NMK-89812-3 Insect res. cry3A Potato BT10 NMK-89175-5Insect res. cry3A Potato BT12 NMK-89601-8 Insect res. cry3A Potato BT16NMK-89167-6 Insect res. cry3A Potato BT17 NMK-89593-9 Insect res. cry3APotato BT18 NMK-89906-7 Insect res. cry3A Potato BT23 NMK-89675-1 Insectres. cry3A Potato EH92-527-1 BPS-25271-9 Modified starch/carbohydrategbss (antisense) Potato HLMT15-15 NA Insect & disease res. cry3A; pvy cpPotato HLMT15-3 NA Insect & disease res. cry3A; pvy cp Potato HLMT15-46NA Insect & disease res. cry3A; pvy cp Potato RBMT15-101 NMK-89653-6Insect & disease res. cry3A; pvy cp Potato RBMT21-129 NMK-89684-1 Insect& disease res. cry3A; plrv orf1; plrv orf2 Potato RBMT21-152 NA Insect &disease res. cry3A; plrv orf1; plrv orf2 Potato RBMT21-350 NMK-89185-6Insect & disease res. cry3A; plrv orf1; plrv orf2 Potato RBMT22-082NMK-89896-6 Insect & disease res.; cry3A; plrv orf1; plrv Glyphosatetol. orf2; cp4 epsps (aroA:CP4) Potato RBMT22-186 NA Insect & diseaseres.; cry3A; plrv orf1; plrv Glyphosate tol. orf2; cp4 epsps (aroA:CP4)Potato RBMT22-238 NA Insect & disease res.; cry3A; plrv orf1; plrvGlyphosate tol. orf2; cp4 epsps (aroA:CP4) Potato RBMT22-262 NA Insect &disease res.; cry3A; plrv orf1; plrv Glyphosate tol. orf2; cp4 epsps(aroA:CP4) Potato SEMT15-02 NMK-89935-9 Insect & disease res. cry3A; pvycp Potato SEMT15-07 NA Insect & disease res. cry3A; pvy cp PotatoSEMT15-15 NMK-89930-4 Insect & disease res. cry3A; pvy cp PotatoSPBT02-5 NMK-89576-1 Insect res. cry3A Potato SPBT02-7 NMK-89724-5Insect res. cry3A Rice 7Crp#242-95-7 Anti-allergy 7crp Rice 7Crp#10 NAAnti-allergy 7crp Rice GM Shanyou 63 NA Insect res. cry1Ab; cry1Ac RiceHuahui-1/TT51-1 NA Insect res. cry1Ab; cry1Ac Rice LLRICE06 ACS-OS001-4Glufosinate tol. bar Rice LLRICE601 BCS-OS003-7 Glufosinate tol. barRice LLRICE62 ACS-OS002-5 Glufosinate tol. bar Rice Tarom molaii + NAInsect res. cry1Ab (truncated) cry1Ab Rice GAT-OS2 Glufosinate tol. barRice GAT-OS3 Glufosinate tol. bar Rice PE-7 Insect res. Cry1Ac Rice7Crp#10 NA Anti-allergy 7crp Rice KPD627-8 High tryptophan OASA1D RiceKPD722-4 High tryptophan OASA1D Rice KA317 High tryptophan OASA1D RiceHW5 High tryptophan OASA1D Rice HW1 High tryptophan OASA1D Rice B-4-1-18Erect leaves semidwarf Δ OsBRI1 Rice G-3-3-22 Semidwarf OSGA2ox1 RiceAD77 Disease res. DEF Rice AD51 Disease res. DEF Rice AD48 Disease res.DEF Rice AD41 Disease res. DEF Rice 13pNasNaatAprt1 Low iron tol.HvNAS1; HvNAAT-A; APRT Rice 13pAprt1 Low iron tol. APRT Rice gHvNAS1-Low iron tol. HvNAS1; HvNAAT-A; gHvNAAT-1 HvNAAT-B Rice gHvIDS3-1 Lowiron tol. HvIDS3 Rice gHvNAAT1 Low iron tol. HvNAAT-A; HvNAAT-B RicegHvNAS1-1 Low iron tol. HvNAS1 Rice NIA-OS006-4 Disease res. WRKY45 RiceNIA-OS005-3 Disease res. WRKY45 Rice NIA-OS004-2 Disease res. WRKY45Rice NIA-OS003-1 Disease res. WRKY45 Rice NIA-OS002-9 Disease res.WRKY45 Rice NIA-OS001-8 Disease res. WRKY45 Rice OsCr11 Anti-allergyModified Cry j Rice 17053 Glyphosate tol. cp4 epsps (aroA:CP4) Rice17314 Glyphosate tol. cp4 epsps (aroA:CP4) Rose WKS82/130-4-1IFD-52401-4 Modified flower color 5AT; bp40 (f3′5′h) Rose WKS92/130-9-1IFD-52901-9 Modified flower color 5AT; bp40 (f3′5′h) Soybean 260-05(G94-1, NA Modified oil/fatty acid gm-fad2-1 (silencing G94-19, G168)locus) Soybean A2704-12 ACS-GM005-3 Glufosinate tol. pat SoybeanA2704-21 ACS-GM004-2 Glufosinate tol. pat Soybean A5547-127 ACS-GM006-4Glufosinate tol. pat Soybean A5547-35 ACS-GM008-6 Glufosinate tol. patSoybean CV127 BPS-CV127-9 Imidazolinone tol. csr1-2 Soybean DAS68416-4DAS68416-4 Glufosinate tol. pat Soybean DP305423 DP-305423-1 Modifiedoil/fatty acid; gm-fad2-1 (silencing ALS herbicide tol. locus); gm-hraSoybean DP356043 DP-356043-5 Modified oil/fatty acid; gm-fad2-1(silencing glyphosate tol. locus); gat4601 Soybean FG72 MST-FG072-3Glyphosate & HPPD tol. 2mepsps; hppdPF W336 Soybean GTS 40-3-2MON-04032-6 Glyphosate tol. cp4 epsps (aroA:CP4) (40-3-2) Soybean GU262ACS-GM003-1 Glufosinate tol. pat Soybean MON87701 MON-87701-2 Insectres. cry1Ac Soybean MON87705 MON-87705-6 Modified oil/fatty acid;fatb1-A (sense & glyphosate tol. antisense); fad2-1A (sense &antisense); cp4 epsps (aroA:CP4) Soybean MON87708 MON-87708-9 Dicamba &glyphosate tol. dmo; cp4 epsps (aroA:CP4) Soybean MON87769 MON-87769-7Modified oil/fatty acid; Pj.D6D; Nc.Fad3; cp4 glyphosate tol. epsps(aroA:CP4) Soybean MON89788 MON-89788-1 Glyphosate tol. cp4 epsps(aroA:CP4) Soybean W62 ACS-GM002-9 Glufosinate tol. bar Soybean W98ACS-GM001-8 Glufosinate tol. bar Soybean MON87754 MON-87754-1 High oildgat2A Soybean DAS21606 DAS-21606 Aryloxyalkanoate & Modified aad-12;pat glufosinate tol. Soybean DAS44406 DAS-44406-6 Aryloxyalkanoate,glyphosate Modified aad-12; & glufosinate tol. 2mepsps; pat SoybeanSYHT04R SYN-0004R-8 Mesotrione tol. Modified avhppd Soybean9582.814.19.1 Insect res. & glufosinate tol. cry1Ac, cry1F, PAT SquashCZW3 SEM-ØCZW3-2 Disease res. cmv cp, zymv cp, wmv cp Squash ZW20SEM-0ZW20-7 Disease res. zymv cp, wmv cp Sugar Beet GTSB77 SY-GTSB77-8Glyphosate tol. cp4 epsps (aroA:CP4); (T9100152) goxv247 Sugar Beet H7-1KM-000H71-4 Glyphosate tol. cp4 epsps (aroA:CP4) Sugar Beet T120-7ACS-BV001-3 Glufosinate tol. pat Sugar Beet T227-1 Glyphosate tol. cp4epsps (aroA:CP4) Sugarcane NXI-1T Drought tol. EcbetA Sunflower X81359Imidazolinone tol. als Sweet PK-SP01 NA Disease res. cmv cp PepperTobacco C/F/93/08-02 NA Oxynil tol. bxn Tobacco Vector 21-41 NA Reducednicotine NtQPT1 (antisense) Tomato 1345-4 NA Delayed ripening/senescenseacc (truncated) Tomato 35-1-N NA Delayed ripening/senescense sam-kTomato 5345 NA Insect res. cry1Ac Tomato 8338 CGN-89322-3 Delayedripening/senescense accd Tomato B SYN-0000B-6 Delayedripening/senescense pg (sense or antisense) Tomato Da SYN-0000DA-9Delayed ripening/senescense pg (sense or antisense) Sunflower X81359Imidazolinone tol. als Tomato Da Dong No 9 NA Modified product NA TomatoF (1401F, h38F, SYN-0000F-1 Delayed ripening/senescense pg (sense orantisense) 11013F, 7913F) Tomato FLAVR SAVR ™ CGN-89564-2 Delayedripening/senescense pg (sense or antisense) Tomato Huafan No 1 NADelayed ripening/senescense anti-efe Tomato PK-TM8805R NA Disease res.cmv cp (8805R) Wheat MON71800 MON-718ØØ-3 Glyphosate tol. cp4 epsps(aroA:CP4) *Argentine, **Polish, # Eggplant

Treatment of genetically modified plants and seeds with compounds of theinvention may result in super-additive or synergistic effects. Forexample, reduction in application rates, broadening of the activityspectrum, increased tolerance to biotic/abiotic stresses or enhancedstorage stability may be greater than expected from just simple additiveeffects of the application of compounds of the invention on geneticallymodified plants and seeds.

Compounds of this invention are also useful in seed treatments forprotecting seeds from invertebrate pests. In the context of the presentdisclosure and claims, treating a seed means contacting the seed with abiologically effective amount of a compound of this invention, which istypically formulated as a composition of the invention. This seedtreatment protects the seed from invertebrate soil pests and generallycan also protect roots and other plant parts in contact with the soil ofthe seedling developing from the germinating seed. The seed treatmentmay also provide protection of foliage by translocation of the compoundof this invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensistoxin or those expressing herbicide resistance such as glyphosateacetyltransferase, which provides resistance to glyphosate. Seedtreatments with compounds of this invention can also increase vigor ofplants growing from the seed.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent. Therefore typically a seedcoating composition of the present invention comprises a biologicallyeffective amount of a compound of Formula 1, an N-oxide or salt thereof,and a film former or adhesive agent. Seed can be coated by spraying aflowable suspension concentrate directly into a tumbling bed of seedsand then drying the seeds. Alternatively, other formulation types suchas wetted powders, solutions, suspoemulsions, emulsifiable concentratesand emulsions in water can be sprayed on the seed. This process isparticularly useful for applying film coatings on seeds. Various coatingmachines and processes are available to one skilled in the art. Suitableprocesses include those listed in P. Kosters et al., Seed Treatment:Progress and Prospects, 1994 BCPC Mongraph No. 57, and references listedtherein.

Compounds of Formula 1 and their compositions, both alone and incombination with other insecticides, nematicides, and fungicides, areparticularly useful in seed treatment for crops including, but notlimited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats,barley, rye and rice), potatoes, vegetables and oilseed rape.

Other insecticides with which compounds of Formula 1 can be formulatedto provide mixtures useful in seed treatment include abamectin,acetamiprid, acrinathrin, amitraz, avermectin, azadirachtin, bensultap,bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, dieldrin, dinotefuran,diofenolan, emamectin, endosulfan, esfenvalerate, ethiprole, etofenprox,etoxazole, fenothiocarb, fenoxycarb, fenvalerate, fipronil, flonicamid,flubendiamide, flufenoxuron, fluvalinate, formetanate, fosthiazate,hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, lufenuron,metaflumizone, methiocarb, methomyl, methoprene, methoxyfenozide,nitenpyram, nithiazine, novaluron, oxamyl, pymetrozine, pyrethrin,pyridaben, pyridalyl, pyriproxyfen, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor, tebufenozide,tetramethrin, thiacloprid, thiamethoxam, thiodicarb, thiosultap-sodium,tralomethrin, triazamate, triflumuron, Bacillus thuringiensisdelta-endotoxins, all strains of Bacillus thuringiensis and all strainsof nucleo polyhedrosis viruses.

Fungicides with which compounds of Formula 1 can be formulated toprovide mixtures useful in seed treatment include amisulbrom,azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole,difenoconazole, dimethomorph, fluazinam, fludioxonil, fluquinconazole,fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole,iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil,paclobutrazole, penflufen, picoxystrobin, prothioconazole,pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole,thiophanate-methyl, thiram, trifloxystrobin and triticonazole.

Compositions comprising compounds of Formula 1 useful for seed treatmentcan further comprise bacteria and fungi that have the ability to provideprotection from the harmful effects of plant pathogenic fungi orbacteria and/or soil born animals such as nematodes. Bacteria exhibitingnematicidal properties may include but are not limited to Bacillusfirmus, Bacillus cereus, Bacillius subtillis and Pasteuria penetrans. Asuitable Bacillus firmus strain is strain CNCM I-1582 (GB-126) which iscommercially available as BioNem™. A suitable Bacillus cereus strain isstrain NCMM I-1592. Both Bacillus strains are disclosed in U.S. Pat. No.6,406,690. Other suitable bacteria exhibiting nematicidal activity areB. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteriaexhibiting fungicidal properties may include but are not limited to B.pumilus strain GB34. Fungal species exhibiting nematicidal propertiesmay include but are not limited to Myrothecium verrucaria, Paecilomyceslilacinus and Purpureocillium lilacinum.

Seed treatments can also include one or more nematicidal agents ofnatural origin such as the elicitor protein called harpin which isisolated from certain bacterial plant pathogens such as Erwiniaamylovora. An example is the Harpin-N-Tek seed treatment technologyavailable as N-Hibit™ Gold CST.

Seed treatments can also include one or more species of legume-rootnodulating bacteria such as the microsymbiotic nitrogen-fixing bacteriaBradyrhizobium japonicum. These inocculants can optionally include oneor more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod)factors produced by rhizobia bacteria during the initiation of noduleformation on the roots of legumes. For example, the Optimize® brand seedtreatment technology incorporates LCO Promoter Technology™ incombination with an inocculant.

Seed treatments can also include one or more isoflavones which canincrease the level of root colonization by mycorrhizal fungi.Mycorrhizal fungi improve plant growth by enhancing the root uptake ofnutrients such as water, sulfates, nitrates, phosphates and metals.Examples of isoflavones include, but are not limited to, genistein,biochanin A, formononetin, daidzein, glycitein, hesperetin, naringeninand pratensein. Formononetin is available as an active ingredient inmycorrhizal inocculant products such as PHC Colonize® AG.

Seed treatments can also include one or more plant activators thatinduce systemic acquired resistance in plants following contact by apathogen. An example of a plant activator which induces such protectivemechanisms is acibenzolar-S-methyl.

The treated seed typically comprises a compound of the present inventionin an amount from about 0.1 g to 1 kg per 100 kg of seed (i.e. fromabout 0.0001 to 1% by weight of the seed before treatment). A flowablesuspension formulated for seed treatment typically comprises from about0.5 to about 70% of the active ingredient, from about 0.5 to about 30%of a film-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

The compounds of this invention can be incorporated into a baitcomposition that is consumed by an invertebrate pest or used within adevice such as a trap, bait station, and the like. Such a baitcomposition can be in the form of granules which comprise (a) activeingredients, namely a biologically effective amount of a compound ofFormula 1, an N-oxide, or salt thereof; (b) one or more food materials;optionally (c) an attractant, and optionally (d) one or more humectants.Of note are granules or bait compositions which comprise between about0.001-5% active ingredients, about 40-99% food material and/orattractant; and optionally about 0.05-10% humectants, which areeffective in controlling soil invertebrate pests at very low applicationrates, particularly at doses of active ingredient that are lethal byingestion rather than by direct contact. Some food materials canfunction both as a food source and an attractant. Food materials includecarbohydrates, proteins and lipids. Examples of food materials arevegetable flour, sugar, starches, animal fat, vegetable oil, yeastextracts and milk solids. Examples of attractants are odorants andflavorants, such as fruit or plant extracts, perfume, or other animal orplant component, pheromones or other agents known to attract a targetinvertebrate pest. Examples of humectants, i.e. moisture retainingagents, are glycols and other polyols, glycerine and sorbitol. Of noteis a bait composition (and a method utilizing such a bait composition)used to control at least one invertebrate pest selected from the groupconsisting of ants, termites and cockroaches. A device for controllingan invertebrate pest can comprise the present bait composition and ahousing adapted to receive the bait composition, wherein the housing hasat least one opening sized to permit the invertebrate pest to passthrough the opening so the invertebrate pest can gain access to the baitcomposition from a location outside the housing, and wherein the housingis further adapted to be placed in or near a locus of potential or knownactivity for the invertebrate pest.

One embodiment of the present invention relates to a method forcontrolling invertebrate pests, comprising diluting the pesticidalcomposition of the present invention (a compound of Formula 1 formulatedwith surfactants, solid diluents and liquid diluents or a formulatedmixture of a compound of Formula 1 and at least one other pesticide)with water, and optionally adding an adjuvant to form a dilutedcomposition, and contacting the invertebrate pest or its environmentwith an effective amount of said diluted composition.

Although a spray composition formed by diluting with water a sufficientconcentration of the present pesticidal composition can providesufficient efficacy for controlling invertebrate pests, separatelyformulated adjuvant products can also be added to spray tank mixtures.These additional adjuvants are commonly known as “spray adjuvants” or“tank-mix adjuvants”, and include any substance mixed in a spray tank toimprove the performance of a pesticide or alter the physical propertiesof the spray mixture. Adjuvants can be surfactants, emulsifying agents,petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers,thickeners or defoaming agents. Adjuvants are used to enhancing efficacy(e.g., biological availability, adhesion, penetration, uniformity ofcoverage and durability of protection), or minimizing or eliminatingspray application problems associated with incompatibility, foaming,drift, evaporation, volatilization and degradation. To obtain optimalperformance, adjuvants are selected with regard to the properties of theactive ingredient, formulation and target (e.g., crops, insect pests).

Among the spray adjuvants, oils including crop oils, crop oilconcentrates, vegetable oil concentrates and methylated seed oilconcentrates are most commonly used to improve the efficacy ofpesticides, possibly by means of promoting more even and uniform spraydeposits. In situations where phytotoxicity potentially caused by oilsor other water-immiscible liquids are of concern, spray compositionsprepared from the composition of the present invention will generallynot contain oil-based spray adjuvants. However, in situations wherephytotoxicity caused by oil-based spray adjuvants is commerciallyinsignificant, spray compositions prepared from the composition of thepresent composition can also contain oil-based spray adjuvants, whichcan potentially further increase control of invertebrate pests, as wellas rainfastness.

Products identified as “crop oil” typically contain 95 to 98% paraffinor naphtha-based petroleum oil and 1 to 2% of one or more surfactantsfunctioning as emulsifiers. Products identified as “crop oilconcentrates” typically consist of 80 to 85% of emulsifiablepetroleum-based oil and 15 to 20% of nonionic surfactants. Productscorrectly identified as “vegetable oil concentrates” typically consistof 80 to 85% of vegetable oil (i.e. seed or fruit oil, most commonlyfrom cotton, linseed, soybean or sunflower) and 15 to 20% of nonionicsurfactants. Adjuvant performance can be improved by replacing thevegetable oil with methyl esters of fatty acids that are typicallyderived from vegetable oils. Examples of methylated seed oilconcentrates include MSO® Concentrate (UAP-Loveland Products, Inc.) andPremium MSO Methylated Spray Oil (Helena Chemical Company).

The amount of adjuvants added to spray mixtures generally does notexceed about 2.5% by volume, and more typically the amount is from about0.1 to about 1% by volume. The application rates of adjuvants added tospray mixtures are typically between about 1 to 5 L per hectare.Representative examples of spray adjuvants include: Adigor® (Syngenta)47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (HelenaChemical Company) polyalkyleneoxide modified heptamethyltrisiloxane andAssist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.

The compounds of this invention can be applied without other adjuvants,but most often application will be of a formulation comprising one ormore active ingredients with suitable carriers, diluents, andsurfactants and possibly in combination with a food depending on thecontemplated end use. One method of application involves spraying awater dispersion or refined oil solution of a compound of the presentinvention. Combinations with spray oils, spray oil concentrations,spreader stickers, adjuvants, other solvents, and synergists such aspiperonyl butoxide often enhance compound efficacy. For nonagronomicuses such sprays can be applied from spray containers such as a can, abottle or other container, either by means of a pump or by releasing itfrom a pressurized container, e.g., a pressurized aerosol spray can.Such spray compositions can take various forms, for example, sprays,mists, foams, fumes or fog. Such spray compositions thus can furthercomprise propellants, foaming agents, etc. as the case may be. Of noteis a spray composition comprising a biologically effective amount of acompound or a composition of the present invention and a carrier. Oneembodiment of such a spray composition comprises a biologicallyeffective amount of a compound or a composition of the present inventionand a propellant. Representative propellants include, but are notlimited to, methane, ethane, propane, butane, isobutane, butene,pentane, isopentane, neopentane, pentene, hydrofluorocarbons,chlorofluorocarbons, dimethyl ether, and mixtures of the foregoing. Ofnote is a spray composition (and a method utilizing such a spraycomposition dispensed from a spray container) used to control at leastone invertebrate pest selected from the group consisting of mosquitoes,black flies, stable flies, deer flies, horse flies, wasps, yellowjackets, hornets, ticks, spiders, ants, gnats, and the like, includingindividually or in combinations.

BIOLOGICAL EXAMPLES OF THE INVENTION

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pests. “Control efficacy” representsinhibition of invertebrate pest development (including mortality) thatcauses significantly reduced feeding. The pest control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A and B for compound descriptions.

Formulation and Spray Methodology for Tests A-D

Test compounds were formulated using a solution containing 10% acetone,90% water and 300 ppm X-77® Spreader Lo-Foam Formula non-ionicsurfactant containing alkylarylpolyoxyethylene, free fatty acids,glycols and isopropanol (Loveland Industries, Inc. Greeley, Colo., USA).The formulated compounds were applied in 1 mL of liquid through a SUJ2atomizer nozzle with ⅛ JJ custom body (Spraying Systems Co. Wheaton,Ill., USA) positioned 1.27 cm (0.5 inches) above the top of each testunit. Test compounds were sprayed at the rates indicated, and each testwas replicated three times.

Test A

For evaluating control of green peach aphid (Myzus persicae (Sulzer))through contact and/or systemic means, the test unit consisted of asmall open container with a 12-15-day-old radish plant inside. This waspre-infested by placing on a leaf of the test plant 30-40 aphids on apiece of leaf excised from a culture plant (cut-leaf method). The aphidsmoved onto the test plant as the leaf piece desiccated. Afterpre-infestation, the soil of the test unit was covered with a layer ofsand.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying of the formulated test compound, each test unit was allowed todry for 1 hour and then a black, screened cap was placed on top. Thetest units were held for 6 days in a growth chamber at 19-21° C. and50-70% relative humidity. Each test unit was then visually assessed forinsect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 2, 5, 7, 8, 9, 10, 13, 14, 15, 18, 19, 20,30, 32, 35, 38 and 39.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 2, 6, 7, 8, 9, 13, 14, 15, 16, 18, 19, 20,35, 38 and 39.

Test B

For evaluating control of cotton melon aphid (Aphis gossypii (Glover))through contact and/or systemic means, the test unit consisted of asmall open container with a 6-7-day-old cotton plant inside. This waspre-infested with 30-40 insects on a piece of leaf according to thecut-leaf method, and the soil of the test unit was covered with a layerof sand.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying, the test units were maintained in a growth chamber for 6 daysat 19° C. and 70% relative humidity. Each test unit was then visuallyassessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 7, 8, 9, 10, 12, 14, 15, 18, 20, 22, 26, 27,30, 32, 35, 38, 39 and 45.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 6, 7, 8, 9, 10, 12, 14, 16, 22, 26, 30, 35,38, 39 and 45.

Test C

For evaluating control of the Western Flower Thrips (Frankliniellaoccidentalis (Pergande)) through contact and/or systemic means, the testunit consisted of a small open container with a 5-7-day-old Soleil beanplant inside.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying, the test units were allowed to dry for 1 hour, and then 22-27adult thrips were added to each unit. A black, screened cap was placedon top, and the test units were held for 6 days at 25° C. and 45-55%relative humidity.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 8 and 14.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 8 and 14.

Test D

For evaluating control of the sweetpotato whitefly (Bemisia tabaci(Gennadius)) through contact and/or systemic means, the test unitconsisted of a small open container with a 12-14-day-old cotton plantinside. Prior to the spray application, both cotyledons were removedfrom the plant, leaving one true leaf for the assay. Adult whiteflieswere allowed to lay eggs on the plant and then were removed from thetest unit. Cotton plants infested with at least 15 eggs were submittedto the test for spraying.

Test compounds were formulated and sprayed at 250 and/or 50 ppm. Afterspraying, the test units were allowed to dry for 1 hour. The cylinderswere then removed, and the units were taken to a growth chamber and heldfor 13 days at 28° C. and 50-70% relative humidity. Each test unit wasthen visually assessed for insect mortality.

Of the compounds of Formula 1 tested at 250 ppm, the following resultedin at least 80% mortality: 7 and 8.

Of the compounds of Formula 1 tested at 50 ppm, the following resultedin at least 80% mortality: 14.

What is claimed is:
 1. A compound selected from Formula 1, an N-oxide orsalt thereof,

wherein Q is

A is CH, or CF; X¹ is —C(R²)═C(R³)—, or —C(R³)═C(R²)—, and X² is O S orNR³; each Z is independently O or S; each R³ is independently H,halogen, cyano, nitro, C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy orC₁-C₄ haloalkoxy; Y³ CR^(5b); R^(5b) is H, halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy or C₁-C₄haloalkoxy; R⁶ is H, NR¹⁵R¹⁶, OR¹⁷, C(═NR¹⁰)R¹¹, C(O)OR²¹, C(O)NR¹⁵R¹⁶,C(O)R²², S(O)_(n)R²³ or Q^(b); or C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted with atleast one R^(x); R⁷ is H or Q^(b); or C₁-C₆ alkyl, C₃-C₆ cycloalkyl,C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted or substituted withat least one R^(x); or R⁶ and R⁷ are taken together with the nitrogenatom to which they are attached to form a 3- to 10-membered ringcontaining ring members selected from carbon atoms and up to 2heteroatoms independently selected from one oxygen atom, one sulfuratom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S) and the sulfuratom ring member is selected from S, S(O) or S(O)₂, said ring beingunsubstituted or substituted with up to 4 R^(x); or R⁶ and R⁷ are takentogether as ═S(O)_(p)R¹⁸R¹⁹ or ═S(═NR²⁰)R¹⁸R¹⁹; each R^(x) isindependently halogen, cyano, nitro, hydroxy, C₁-C₆ alkyl, C₁-C₆haloalkyl, C₃-C₆ cycloalkyl, C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₃-C₆cycloalkoxy, C(═NR¹⁰)R¹¹, C(O)OR²¹, C(O)NR¹⁵R¹⁶, OC(O)R²², NR²⁵R²⁶,NR²⁴C(O)R²², C(O)R²², S(O)_(n)R²³, Si(R²⁸)₃, OSi(R²⁸)₃ or Q^(b); eachR¹⁰ is independently OR¹², S(O)_(n)R¹³ or NHR¹⁴; each R¹¹ isindependently H; or C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl orC₂-C₆ alkynyl, each unsubstituted or substituted with at least oneR^(x); or C₁-C₆ alkoxy, C₁-C₆ haloalkoxy, C₃-C₆ cycloalkoxy, C(O)OR²¹,C(O)NR¹⁵R¹⁶; C(O)R²² or Q^(b); each R¹² is independently C₁-C₄ alkyl,C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C(O)R²², S(O)_(n)R¹³ or Q^(b); eachR¹³ is independently C₁-C₄ alkyl or C₁-C₄ haloalkyl; R¹⁴ is C₁-C₄ alkyl,C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C(O)R²² or C(O)OR²¹; or phenyl,unsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; each R¹⁵ is independently H, C₁-C₆ alkyl, C₁-C₄ haloalkyl,C(O)R²⁷ or S(O)₂R²⁷; or phenyl or a 5- or 6-membered heterocyclicaromatic ring, each unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy and C₁-C₄ haloalkoxy; each R¹⁶ is independently H, C₁-C₆ alkyl orC₁-C₄ haloalkyl; or R¹⁵ and R¹⁶ are taken together with the nitrogenatom to which they are attached to form a 3- to 7-membered ringcontaining ring members selected from carbon atoms and up to 2heteroatoms independently selected from one oxygen atom, one sulfuratom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S) and the sulfuratom ring member is selected from S, S(O) or S(O)₂, said ring beingunsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; R¹⁷ is C₁-C₄ alkyl, C₃-C₆ cycloalkyl or C₁-C₄ haloalkyl; orphenyl, unsubstituted or substituted with at least one substituentindependently selected from the group consisting of halogen, cyano,nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy andC₁-C₄ haloalkoxy; each R¹⁸ is independently C₁-C₄ alkyl or C₁-C₄haloalkyl; or phenyl, unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy and C₁ 1C₄ haloalkoxy; each R¹⁹ is independently C₁-C₄ alkyl orC₁-C₄ haloalkyl; or phenyl, unsubstituted or substituted with at leastone substituent independently selected from the group consisting ofhalogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or R¹⁸ and R¹⁹ are taken togetherwith the sulfur atom to which they are attached to form a ring; R²⁰ isH, cyano, C₁-C₄ alkyl, C₁-C₄ haloalkyl or C(O)R²²; or phenyl,unsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; each R²¹ is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl,C₃-C₆ cycloalkyl or C₃ ⁻C₆ halocycloalkyl; or phenyl, unsubstituted orsubstituted with at least one substituent independently selected fromthe group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R²²is independently C₁-C₄ alkyl, C₁-C₄ haloalkyl, C₃-C₆ cycloalkyl or C₃-C₆halocycloalkyl; or phenyl, unsubstituted or substituted with at leastone substituent independently selected from the group consisting ofhalogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl,C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R²³ is independently C₁-C₄alkyl, C₁-C₄ haloalkyl, C₃-C₆ cycloalkyl, C₃-C₆ halocycloalkyl, C₃-C₆cycloalkylalkyl or C₃-C₆ halocycloalkylalkyl; or phenyl, unsubstitutedor substituted with at least one substituent independently selected fromthe group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R²⁴is independently C₁-C₄ alkyl; each R²⁵ is independently H, C₁-C₄ alkylor C₁-C₄ haloalkyl; or phenyl, unsubstituted or substituted with atleast one substituent independently selected from the group consistingof halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R²⁶ is independentlyC₁-C₄ alkyl or C₁-C₄ haloalkyl; or phenyl, unsubstituted or substitutedwith at least one substituent independently selected from the groupconsisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl,C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or R²⁵ and R²⁶ areindependently taken together with the nitrogen atom to which they areattached to form a 3- to 7-membered ring containing ring membersselected from carbon atoms and up to 2 heteroatoms independentlyselected from one oxygen atom, one sulfur atom, and up to 2 nitrogenatoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S) and the sulfur atom ring member isselected from S, S(O) or S(O)₂, said ring being unsubstituted orsubstituted with at least one substituent independently selected fromthe group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; each R²⁷is independently C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, C₁-C₆haloalkoxy or NR²⁹R³⁰; or phenyl or a 5- or 6-membered heterocyclicaromatic ring, each unsubstituted or substituted with at least onesubstituent independently selected from the group consisting of halogen,cyano, nitro, C₁-C₄ alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄alkoxy and C₁-C₄ haloalkoxy; each R²⁸ is independently C₁-C₆ alkyl,C₃-C₆ cycloalkyl or phenyl; each R²⁹ is independently H or Q^(b); orC₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, eachunsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; each R³⁰ is independently H or Q^(b); or C₁-C₆ alkyl, C₃-C₆cycloalkyl, C₂-C₆ alkenyl or C₂-C₆ alkynyl, each unsubstituted orsubstituted with at least one substituent independently selected fromthe group consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; or R²⁹and R³⁰ are taken together with the nitrogen atom to which they areattached to form a 3- to 10-membered ring containing ring membersselected from carbon atoms and up to 2 heteroatoms independentlyselected from one oxygen atom, one sulfur atom, and up to 2 nitrogenatoms, wherein up to 2 carbon atom ring members are independentlyselected from C(═O) and C(═S) and the sulfur atom ring member isselected from S, S(O) or S(O)₂, said ring being unsubstituted orsubstituted with up to 4 substituents independently selected from thegroup consisting of halogen, cyano, nitro, C₁-C₄ alkyl, C₃-C₆cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄ haloalkoxy; eachQ^(b) is independently phenyl, a 5- or 6-membered heterocyclic aromaticring or a 3- to 6-membered heterocyclic non-aromatic ring, each ringcontaining ring members selected from carbon atoms and up to 2heteroatoms independently selected from one oxygen atom, one sulfuratom, and up to 2 nitrogen atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O) and C(═S) and the sulfuratom ring member is selected from S, S(O) or S(O)₂, each ringunsubstituted or substituted with at least one substituent independentlyselected from the group consisting of halogen, cyano, nitro, C₁-C₄alkyl, C₃-C₆ cycloalkyl, C₁-C₄ haloalkyl, C₁-C₄ alkoxy and C₁-C₄haloalkoxy; each n is independently 0, 1 or 2; and p is 1 or
 2. 2. Acomposition comprising a compound of claim 1 and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents, said composition optionally furthercomprising at least one additional biologically active compound oragent.
 3. The composition of claim 2 wherein the at least one additionalbiologically active compound or agent is selected from the groupconsisting of abamectin, acephate, acequinocyl, acetamiprid,acrinathrin, afidopyropen, amidoflumet, amitraz, avermectin,azadirachtin, azinphos-methyl, benfuracarb, bensultap, bifenthrin,bifenazate, bistrifluron, borate, buprofezin, carbaryl, carbofuran,cartap, carzol, chlorantraniliprole, chlorfenapyr, chlorfluazuron,chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clofentezin,clothianidin, cyantraniliprole, cyclaniliprole, cycloprothrin,cycloxaprid, cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, diafenthiuron, diazinon,dicloromezotiaz, dieldrin, diflubenzuron, dimefluthrin, dimehypo,dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, etofenprox, etoxazole, fenbutatin oxide,fenitrothion, fenothiocarb, fenoxycarb, fenpropathrin, fenvalerate,fipronil, flometoquin, flonicamid, flubendiamide, flucythrinate,flufenerim, flufenoxuron, flufenoxystrobin, flufensulfone, fluorpyram,flupiprole, flupyradifurone, fluvalinate, tau-fluvalinate, fonophos,formetanate, fosthiazate, halofenozide, heptafluthrin, hexaflumuron,hexythiazox, hydramethylnon, imidacloprid, indoxacarb, insecticidalsoaps, isofenphos, lufenuron, malathion, meperfluthrin, metaflumizone,metaldehyde, methamidophos, methidathion, methiodicarb, methomyl,methoprene, methoxychlor, metofluthrin, monocrotophos, monofluthrin,methoxyfenozide, nitenpyram, nithiazine, novaluron, noviflumuron,oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone,phosmet, phosphamidon, pirimicarb, profenofos, profluthrin, propargite,protrifenbute, pyflubumide, pymetrozine, pyrafluprole, pyrethrin,pyridaben, pyridalyl, pyrifluquinazon, pyriminostrobin, pyriprole,pyriproxyfen, rotenone, ryanodine, silafluofen, spinetoram, spinosad,spirodiclofen, spiromesifen, spirotetramat, sulprofos, sulfoxaflor,tebufenozide, tebufenpyrad, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethrin, tetramethylfluthrin, thiacloprid,thiamethoxam, thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin,triazamate, trichlorfon, triflumezopyrim, triflumuron, all strains ofBacillus thuringiensis, entomopathogenic bacteria, all strains of Nucleopolyhedrosis viruses, entomopathogenic viruses and entomopathogenicfungi.
 4. The composition of claim 3 wherein the at least one additionalbiologically active compound or agent is selected from the groupconsisting of abamectin, acetamiprid, acrinathrin, afidopyropen,amitraz, avermectin, azadirachtin, benfuracarb, bensultap, bifenthrin,3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide,buprofezin, carbaryl, cartap, chlorantraniliprole, chlorfenapyr,chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole,cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin,zeta-cypermethrin, cyromazine, deltamethrin, dicloromezotiaz, dieldrin,dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenitrothion, fenothiocarb,fenoxycarb, fenvalerate, fipronil, flometoquin, flonicamid,flubendiamide, flufenoxuron, flufenoxystrobin, flufensulfone,flupiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate,heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb,lufenuron, meperfluthirn, metaflumizone, methiodicarb, methomyl,methoprene, methoxyfenozide, metofluthrin, monofluthrin, nitenpyram,nithiazine, novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin,pyridaben, pyridalyl, pyriminostrobin, pyriproxyfen, ryanodine,spinetoram, spinosad, spirodiclofen, spiromesifen, spirotetramat,sulfoxaflor, tebufenozide, tetramethrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tralomethrin, tetramethylfluthrin,triazamate, triflumezopyrim, triflumuron, all strains of Bacillusthuringiensis and all strains of Nucleo polyhedrosis viruses.
 5. Amethod for controlling an invertebrate pest comprising contacting theinvertebrate pest or its environment with a biologically effectiveamount of a compound of claim
 1. 6. A treated seed comprising a compoundof claim 1 in an amount of from about 0.0001 to 1% by weight of the seedbefore treatment.